An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval (Late Devonian) in the Moravian Karst (Czech Republic) and Kellerwald (Germany)

TOMÁŠ WEINER, JIØÍ KALVODA, TOMÁŠ KUMPAN, EBERHARD SCHINDLER & DANIEL ŠIMÍÈEK

Rapid and profound changes in Earth surface environments and biota across the Frasnian-Famennian (Fr-Fa) boundary are well known and related to one of the five most severe mass extinction events in Earth history. Here, we present sedimentological, biostratigraphical, petrophysical (gamma-ray spectrometry, magnetic susceptibility) and geochem- ical (X-ray fluorescence) data from environmentally distinct sections in the Moravian Karst (Czech Republic) and com- pare them with the Steinbruch Schmidt section in the Kellerwald (Rheinisches Schiefergebirge, Germany). Both areas were located at the southern margin of Laurussia. The studied sections span the interval from the Lower or Upper rhenana to the Palmatolepis minuta minuta or younger conodont zones and the foraminiferal Eonodosaria evlanensis Zone and Eonodosaria evlanensis-Quasiendothyra communis Interzone including high resolution biozonation of the Fr-Fa boundary interval. In the Moravian Karst pure limestone facies of an inclined carbonate ramp reflect the world- wide trend in the widespread occurrence of calcimicrobes during upper Frasnian and lower Famennian. Geochemical and petrophysical data show a decrease in grain size of the siliciclastic supply and carbonate productivity in the Kellwasser Event intervals probably due to a deepening and correlate with maximum flooding surfaces and highstand system tracts in the Steinbruch Schmidt. Certain differences in some geochemical proxies between the Moravian Karst

and Steinbruch Schmidt are due to lower carbonate dilution of the latter. Significant Zr, TiO2,MnorFe2O3 enrichments may indicate the influence of volcanic sources in the studied Moravian Karst Fr-Fa sections. • Key words: Frasnian-Famennian boundary, Kellwasser Events, conodont and foraminifer biostratigraphy, microfacies, gamma-ray spectrometry, magnetic susceptibility, element geochemistry.

WEINER, T., KALVODA, J., KUMPAN, T., SCHINDLER,E.&ŠIMÍČEK, D. 2017. An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval (Late Devonian) in the Moravian Karst (Czech Republic) and Kellerwald (Ger- many). Bulletin of Geosciences 92(2), 257–281 (9 figures, 3 tables, electronic supplementary appendix). Czech Geologi- cal Survey, Prague. ISSN 1214-1119. Manuscript received September 19, 2016; accepted in revised form June 13, 2017; published online June 30, 2017; issued June 30, 2017.

Tomáš Weiner, Jiří Kalvoda & Tomáš Kumpan, Department of Geological Sciences, Masaryk University, Kotlářská 2, 611 37 Brno, Czech Republic; [email protected], [email protected], [email protected] • Eberhard Schindler, Senckenberg Forschungsinstitut und Naturmuseum Frankfurt, Senckenberganlage 25, 60325 Frankfurt am Main, Germany; [email protected] • Daniel Šimíček, Department of Geology, Palacký University, 17. listopadu 12, 772 00 Olomouc, Czech Republic; [email protected]

The end-Frasnian Kellwasser Events (KWE) and the the lower part of the Upper rhenana Zone, whereas the Frasnian-Famennian (Fr-Fa) boundary are well known UKE represents the upper part of the linguiformis Zone for their linkage with one of the five most intensive mass (Ziegler & Sandberg 1990, Schindler 1990b, Feist & extinctions of the Phanerozoic (McLaren 1970, Hallam Schindler 1994). & Wignall 1997, House 2002, Racki 2005, McGhee The Givetian-Frasnian coral-stromatoporoid reef eco- 2013). The series of extinctions collectively comprise systems were significantly affected right from the begin- the Kellwasser Crisis which represents rather long time ning of the Kellwasser Crisis slightly prior to the onset of interval (1 my in total) including the Lower and Upper the LKE (McGhee 1996, Kiessling et al. 2000, Copper Kellwasser Events (LKE and UKE) (Gereke & Schindler 2002) and various groups, such as trilobites, cephalopods, 2012). According to the standard conodont zonation tentaculitoids, conodonts, brachiopods and some terrestrial (sensu Ziegler & Sandberg 1990), the LKE is assigned to biota suffered significant losses before the end of the UKE

DOI 10.3140/bull.geosci.1636 257 Bulletin of Geosciences • Vol. 92, 2, 2017 in the uppermost Frasnian (Schindler 1990a, b; McGhee diagenetic history (e.g. Ellwood et al. 2000; Ruffell & 1996; Walliser 1996; Gereke 2007; McGhee 2013; Huang Worden 2000; Lüning et al. 2003; Halgedahl et al. 2009; & Gong 2016). Among others, these authors discussed vari- da Silva et al. 2009, 2013; Bábek et al. 2010, 2013; ous causes of the extinctions, including climatic oscilla- Koptíková et al. 2010; Whalen & Day 2010). When com- tions (Joachimski & Buggisch 2002, Joachimski et al. bined with element geochemistry data, the interpretative 2002) connected with astronomical forcing (De power of GRS and/or MS for genetic stratigraphy greatly Vleeschouwer et al. 2014), volcanic, tectonic and hydro- increases, as was demonstrated in several recent papers ad- thermal activity (Algeo et al. 1995; Murphy et al. 2000; dressing the Devonian-Carboniferous boundary (Kumpan Joachimski et al. 2001; Racki et al. 2002; Pujol et al. 2006; et al. 2014a, b; 2015; Bábek et al. 2016) and the Givetian- Riquier et al. 2005, 2006; Bond et al. 2013; George et al. Frasnian boundary (Devleeschouwer et al. 2015). The 2014), and impacts of extraterrestrial bodies (cf. McLaren petrophysical record of the Fr-Fa boundary was discussed 1970; Racki 2005, 2012). A multicausal scenario of earth- in several papers mostly providing data either on MS (e.g. bound mechanisms is currently accepted rather than the Crick et al. 2002, Hladil et al. 2006, Whalen & Day cosmic disasters (cf. Racki 2005; Schindler 1990a, b; see 2010), GRS (Hladil 2002, Bond & Zatoń 2003, Hladil et also House 2002; McGhee 2013). The Kellwasser Events al. 2006, Bábek et al. 2007, Bond et al. 2013) or on stable are thought to be connected with prevailing hypoxic con- isotopes and elemental geochemistry (e.g. Joachimski & ditions, which are supposed to be the result of Buggisch 1993, Yudina et al. 2002, Riquier et al. 2005, eutrophication triggered by an increased input of nutrients George et al. 2014). Multi-proxy data combining the (Algeo et al. 1995; Murphy et al. 2000; Joachimski et al. petrophysical and geochemical signature of this interval 2001; Racki et al. 2002; Pujol et al. 2006; Riquier et al. are, however, rare (Racki et al. 2002, Bond et al. 2004, 2005, 2006; Bond et al. 2013; George et al. 2014; Whalen et al. 2015). Rakociński et al. 2016). In this paper, we provide new data on the Fr-Fa interval The LKE and UKE (see Walliser 1996) were recorded in three previously unpublished sections (Fig. 1) in the in various sections over the globe (Feist 1985, Schindler Moravian Karst (Moravo-Silesian Zone of the Bohemian 1990b, Wendt & Belka 1991, Lazreq 1999, Over 2002, Massif, Czech Republic) including conodont and Yudina et al. 2002, Chen et al. 2005, George et al. 2014, foraminifer biostratigraphy, microfacies analysis, field Dopieralska et al. 2016). In some sections, however, the GRS, MS and bulk-rock element geochemistry. They are Fr-Fa boundary is coupled with hiatuses, unconformities correlated with the Steinbruch Schmidt section (Keller- and distinctive facies changes (e.g. Bratton et al. 1999, wald, Germany) which was studied in the same way using Alekseev et al. 1996, Chen & Tucker 2004, Bond & petrophysical and geochemical tools. This section exposes Wignall 2008, Zatoń et al. 2014). lithologically distinctive KWE horizons and represents the Riquier et al. (2006) proposed different causes of an- former auxiliary stratotype which is – compared to the oxia in both Kellwasser Events. The LKE anoxia were in- stratotype Coumiac section – much thicker. The aim of our terpreted as the result of increased primary productivity, integrated stratigraphic study is to test correlative potential enhanced by land-derived nutrient loading, whereas the of the KWE sections without distinctive lithological UKE was conceived as the result of the onset of oxy- changes and with less accurate resolution in bio- gen-impoverished bottom water in the deepest part of the stratigraphic time control. ocean, due to episodic water stratification during the maxi- mum Frasnian transgression. However, the effect of in- creased land-plant growth combined with stronger weather- Geological settings ing (soils) and nutrient influx was considered as significant for the entire Kellwasser Crisis (Algeo et al. 1995, Algeo & The Moravian sections are representative of a vast carbon- Scheckler 1998). ate platform extending from eastern Moravia to southeast- Multi-proxy stratigraphic analysis based on petro- ern Poland (Racki et al. 2002, Bábek et al. 2007). Moravia, physical gamma-ray spectrometry (GRS) and magnetic Poland and the Kellerwald area were located in an epiconti- susceptibility (MS) properties of sedimentary successions nental basin at the Rhenohercynian margin of Laurussia proved a useful approach to stratigraphic correlation and (Franke 1995, 2002; Kalvoda et al. 2008). The succession palaeoenvironmental analysis of key stratigraphic intervals in Steinbruch Schmidt was deposited on a submarine rise during the Palaeozoic. The main benefits of the GRS and (Fig. 1), below the wave-base level, and consists of con- MS techniques are the rapid and inexpensive acquisition of densed pelagic cephalopod limestones consisting of large quantitative datasets and the well-studied causal rela- dark-grey to black limestones, marls and shales of the Kell- tionships between measured parameters and sedimentary wasser intervals (Buggisch 1972; Schindler 1990a, b; 1993). processes, such as detrital input into carbonate platforms, The late Frasnian–early Famennian sedimentary successions redox conditions at the sediment-water interface and exposed at Hády (GPS 49° 13´8˝ N; 16° 40´20.7˝ E),

258 TomᚠWeiner et al. • An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval

A D

B

C

Figure 1. A – localization of studied areas in Central Europe.•B–Late Devonian palaeogeographic and palaeoenvironmental scheme of the western Rheinisches Schiefergebirge with location of Steinbruch Schmidt. After Meischner (1971).•C–schematic map of outcrop and subsurface facies of the Upper Devonian Carbonate platform of the Moravosilesian Basin. Modified after Bábek et al. (2007).•D–location of investigated sections in the southern part of the Moravian Karst.

Šumbera (49° 13´37.7˝ N; 16° 40´23.9˝ E) and Lesní lom ples were macerated in 15% solution of acetic acid. Insol- sections (GPS 49° 13´28.89˝ N; 16° 41´44.79˝ E) are uble residues were separated after the dissolution process located on the outskirts of Brno. These sections comprise using a 0.125 mm mesh size. Standard conodont zones based relatively pure limestones deposited on a carbonate ramp on Ziegler (1962, 1969), Ziegler & Sandberg (1990) and (Hladil et al. 1991), which, during the Famennian, progres- revised Famennian conodont zones of Spalletta et al. sively developed into a NW-SE-oriented halfgraben with (2017) are used in this paper. For further reading, we refer the deposition of hemipelagic nodular limestones and car- to Fig. 2 for correlation of the three previously published bonate turbidites (Kalvoda 1998, Kalvoda et al. 2008). Co- conodont zonations in the lower Famennian. In consistence eval interval was studied in the Moravian Karst in two lo- with many other researches, we cite the zones of Ziegler & calities. The Lesní lom section, investigated by Hladil et al. Sandberg (1990) as Lower, Middle, Upper and Uppermost (1991), was quarried out and Šumbera sections studied by instead of Early, Middle, Late and Latest (see Spalletta et the previous authors (Hladil & Kalvoda 1993a, Streitová al. 2017). 1994, Racki et al. 2002) were covered and as there were no A total of 191 field GRS assays were measured at the coordinates given it was not possible to indentify them with logged sections at 10 to 25 cm thick intervals, depending the section presented in this paper. on section thickness and required detail (Lesní lom: 48 points, Hády: 42 points, Šumbera: 56 points, Steinbruch Schmidt: 45 points). The GRS data were collected using Materials and methods a RS-230 Super Spec portable spectrometer (Radiation Solutions, Inc., Canada) witha2×2˝(103 cm3) The profiles were logged in a bed-by-bed manner for micro- bismuthgermanate (BGO) scintillation detector. The assay facies characteristics. A total of 75 samples for microfacies time was set to 240 s, which is sufficient for carbonate analysis were taken at random intervals (see Figs 3–5). rocks (e.g. Hladil et al. 2006). The counts per second in the Polished sections and standard-sized thin-sections selected energy windows were automatically converted to (27 × 46 mm) were prepared. Thin-sections were studied concentrations of K (%), U (ppm) and Th (ppm) by the in- using a polarising microscope Nikon Eclipse 80i connected struments. The computed (or “clay”) gamma-ray (CGR), to a Nikon DS-F1 digital camera. A total of 47 conodont which is used as a good proxy of the sum of clay fraction in samples (weight between 1–4 kg) were analysed. The sam- carbonates, was calculated from the spectral values using

259 Bulletin of Geosciences • Vol. 92, 2, 2017 the formula CGR [API] = Th [ppm]·3.93 + K [%]·16.32 packstones. Shallow-water fauna (brachiopods, bivalves, (Rider 1999). crinoids, gastropods, trilobites, corals) is restricted, both Rock samples for bulk MS measurements were col- environmentally and in numbers whereas pelagic/nektonic lected at 3 (Moravian Karst) to 5 cm (Steinbruch Schmidt) elements dominate, including goniatites, orthocone cephalo- vertical step intervals and then measured with a laboratory pods, homoctenids, and entomozoaceans. The latter two KLY-4S kappabridge (Agico, Czech Republic; magnetic groups are well preserved in the KW intervals and show field intensity of 300 Am–1, operating frequency of 920 Hz, mass-occurrences in distinct beds. Relatively abundant lin- sensitivity of 4·10–8 SI). Mass-specific MS data expressed gulid brachiopods and especially “buchiolid” bivalves can in m3·kg–1 were used. A total of 599 MS samples (Lesní be found. Lingulids can easily be transported by drifting, lom: 144 samples, Hády: 146 samples, Šumbera: 162, but are also considered to be tolerant to low-oxygen condi- Steinbruch Schmidt: 147) were measured. tions (e.g. Bond & Zatoń 2003, Marynowski et al. 2011 Rock samples used for the MS measurements were pul- from lower Famennian strata; Posenato et al. 2014 across verised in an agate mortar down to < 63 μm fraction. The the Permian-Triassic boundary). For the group of “buchi- powder was placed in plastic cells with a Mylar foil bottom olid” bivalves the same holds true – Grimm (1998) who re- and analysed by a Delta Premium (Innov-X, USA) energy vised many taxa of “Buchiola” even suspected a chemo- dispersive X-ray fluorescence (EDXRF) spectrometer for trophic mode of life, at least for some taxa of the group. 240 seconds using the Geochem VANAD mode. The Above the Fr-Fa boundary, fossils are much less abundant EDXRF data, expressed in counts per seconds (cps), were in the Famennian. calibrated by independent inductively coupled plasma The rocks are extremely rich in condonts; Ziegler & mass spectrometry (ICP-MS) analysis (total digestion) of Sandberg (1990) reported up to 11,200 specimens/kg from 30 samples by the ACME accredited analytical laboratory, the linguiformis Zone – the number of conodonts decreases Vancouver, Canada. Linear regression functions of the in the Famennian, especially immediately above the EDXRF signal (cps) vs. ICP-MS concentrations were used UKWI, but is still up to 2,500 per kilogram in the Middle as the calibration equations to convert the cps data to wt% crepida Zone (Schülke 1995). The palmatolepid-poly- and ppm, while the correlation coefficients (R2) indicated gnathid conodont biofacies dominates – icriodids only in- the sensitivity of the EDXRF method (Tab. 1) crease in number in the final interval of the KW Crisis close to the Fr-Fa boundary (e.g. Sandberg et al. 1988, Ziegler & Sandberg 1990, Schindler 1990b, Schülke Biostratigraphy and facies/microfacies 1995); similar observations have been made in other areas description and interpretation around the Fr-Fa boundary (e.g. in the Polish Holy Cross of the Steinbruch Schmidt section Mountains by Szulczewski 1989, Matyja & Narkiewicz 1992, Racki et al. 2002; in the area of the type locality of Biostratigraphy the Fr-Fa boundary in the French Montagne Noire by Gi- rard 1995, Girard & Feist 1997). The typical conodonts of At Steinbruch Schmidt, 7.5 m of Late Devonian cephalo- the late Frasnian and the early Famennian are present. As it pod limestones are exposed including the Lower and Upper would lead much too far to mention most of the taxa occur- Kellwasser Event intervals (LKWI and UKWI, respecti- ring in the time interval under consideration, only a few vely). It is one of the classical localities and many resear- critical ones shall be highlighted. The data mainly come chers studied the abandoned quarry (e.g. Buggisch 1972; from the papers of Sandberg et al. (1988), Ziegler & Sandberg et al. 1988; Ziegler & Sandberg 1990; Schindler Sandberg (1990) and Schülke (1995); they studied the 1990a, b; Schülke 1995; Walliser 1996; Casier & Lethiers conodonts extensively in the Steinbruch Schmidt section – 1998; Devleeschouwer et al. 2002; Kaufmann et al. 2004; for details and preceeding conodont research we refer to Pujol et al. 2006; Dopieralska et al. 2016). The section re- these publications. presents former parastratotype for the Fr-Fa boundary (for Characteristic taxa for the Frasnian are ancyrodellids discussion of the boundary see Klapper et al. 1993). The (e.g. Ancyrodella nodosa, Ancyrodella curvata), thickness of the LKWI is up to 0.45 m and that of the Palmatolepis rhenana rhenana, Pa. nasuta and Ancyroides UKWI is up to 0.4 m; the limestones between the LKWI tsiensi through the late Lower rhenana to the Upper and UKWI measure up to 2.6 m. The age of the strata ranges rhenana to linguiformis zones, and Pa. bogartensis (for- from the late Lower rhenana Zone to the rhomboidea merly Pa. rotunda) in the Upper rhenana and linguiformis (= Pa. rhomboidea to Pa. gracilis) Zone. Here, we deal zones. The diagnostic taxon of the linguiformis Zone with a succession from close to the top of the Lower rhe- (Pa. linguiformis) is – unlike in many areas around the nana Zone to the Upper triangularis (= Pa. minuta minuta) globe – abundant in the Steinbruch Schmidt section. After Zone. The rocks represent pelagic limestones mostly com- the severe loss of conodont taxa referred to by many au- prising mudstones and wackestones with less common thors, a restricted number of taxa carried on in the basal

260 TomᚠWeiner et al. • An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval

Famennian: Palmatolepis triangularis and Pa. subperlo- bata occur immediately above the Fr-Fa boundary in the Lower triangularis (= Pa. subperlobata to Pa. tri- angularis) Zone, Pa. delicatula and Pa. claki enter in the Middle triangularis (= Pa. delicatula platys) Zone; Polygnathus brevilaminus is abundant above the Fr-Fa boundary – only very few specimens are reported from the Upper rhenana Zone (Ziegler & Sandberg 1990) and the linguiformis Zone (Schülke 1995 – one questionable speci- men). Two taxa indicating the short time interval just be- low and above the Fr-Fa boundary are known from the sec- tion: Palmatolepis praetriangularis and Ancyroides ubiquitus – the latter was found in the last limestone bed below the Fr-Fa boundary (Schindler 1990b). Besides the conodonts, fossils of other faunal groups are present in the Steinbruch Schmidt section, which indi- cate distinct levels within the Fr-Fa interval. Mass occur- rences of Homoctenus ultimus, the last representative of the homoctenid tentaculitoids prior to their disappearance, are known from the black limestone beds of the UKWI and the grey limestones underneath; H. tenuicinctus is present in the LKWI (Schindler 1990b). From the basal bed of the Famennian, two specimens of Homoctenus sp. have been recognized in a thin-section; although there is a report from China of homoctenids reaching as high as the Famennian rhomboidea (= Pa. rhomboidea to Pa. gracilis) Zone – and a dacryoconarid Styliolina specimen even higher (Li 2000), this is one of the rare cases when homoctenids Figure 2. Upper Frasnian and lower Famennian conodont zones. Cor- relation between three lower Famennian conodont zonations of Ziegler cross the Fr-Fa boundary for a short time (Schindler 1990a, b, (1962, 1969), Ziegler & Sandberg (1990) and Spalletta et al. (2017) is 2012; Over 2002 also reported a few specimens of provided. After Spalletta et al. (2017). Homoctenus above the Fr-Fa boundary from the Northern Appalachian Basin in New York State). Very good indica- tors for the position in the lower part of the UKWI are two parts of the section, characteristic developments can entomozoacean ostracods: 1) Entomoprimitia kayseri is be observed which may be regarded as ‘Time- very abundant in the lower black limestone bed; and 2) Specific Facies’ (TSF; e.g. the patterns of the two KWI E. splendens, a perfect index fossil, is known only from themselves, the beds below them or the strata right above the basal UKWI (Groos-Uffenorde & Schindler 1990, the UKWI). TSF-phenomena have been introduced Schindler 1990b). Both taxa can be traced and correlated by Walliser (1984a, b, 1986) and may be tools for strati- over long distances (Schindler 1993); Olempska (2002) graphic assignment and/or widespread correlation (for reported both taxa from the Polish Holy Cross Moun- further reading and cited literature see Brett et al. 2012). tains. Among the trilobites, some taxa are important to Application of TSF in the Steinbruch Schmidt section be mentioned – with one exception (see following para- has been demonstrated by Schindler (1990b, 1993), graph), they are not present in the oxygen-depleted Over & Schindler (2003) and Gereke & Schindler Kellwasser Event intervals (KWI) themselves: (2012). Palpebralia brecciae can be used to recognize the The KWI themselves are developed in a form typical of linguiformis Zone in cases where conodonts are absent – the pelagic deeper-water settings on submarine rises. The wide correlation of the taxon is possible (for details see black limestones are enriched in fossils and often display Feist & Schindler 1994). lamination at mm-scale. Benthic fossils are very rare (due to O2-depletion) – probably with the exception of “buchiolid” bivalves and a rare find of a trilobite fragment Facies and microfacies in the LKWI (Schindler 1993). Concerning the topic of benthic organisms in O2-depleted environments we refer to In the Steinbruch Schmidt section, the pelagic limestones Rakociński et al. (2016) and literature therein – see also mostly consist of mudstones/wackestones. In particular above.

261 Bulletin of Geosciences • Vol. 92, 2, 2017

Šumbera composite section

Figure 3. Lithology, microfacies, conodont and foraminifer biostratigraphy of the Šumbera section. Abbreviations: Ca – calcarenite, Cl – calcilutite, Cr – calcirudite, Cs – calcisiltite, F – fine-grained, M – medium-grained, C – coarse-grained. Designations “V2-xx” (e.g. V2-7, V2-22) represent selected conodont and thin-section samples.

Biostratigraphy and facies/microfacies quina). This interval spans to the upper part of the lingui- description and interpretation formis Zone to the Pa. subperlobata Zone. Palmatolepis of Moravian Karst sections subperlobata, defining the base of the Famennian (e.g. Klapper 2007, Spalletta et al. 2017), was found in the sam- Conodont biostratigraphy ple V2-26 and Pa. cf. subperlobata was obtained from the sample V2-27. Other taxa from the sample V2-27 suggest The Šumbera section is composed of four laterally correl- Frasnian age, as documented by Pa. gigas gigas. Various ated outcrops (Fig. 3). Frasnian strata about 1.3 m thick are polygnathids (e.g. Polygnathus brevilaminus, Po. webbi), exposed in the lower part of the succession. Owing to the icriodids (Icriodus alternatus) and ancyrodellids (Ancyro- low number of conodonts recovered, the lowermost part of della curvata) were found in this sample. this interval (below sample V2-19) was assigned to the Up- The Pa. triangularis Zone (sensu Spalletta et al. 2017) per rhenana or even lower Frasnian zones of the standard seems to be absent or developed in very reduced thickness conodont zonation (sensu Ziegler & Sandberg 1990). The (below the sampling resolution). The Pa. subperlobata overlying strata belong to the Upper rhenana to linguifor- Zone (sample V2-26) is thus overlain by an approximately mis zones as documented by the occurrence of various taxa 0.25 to 0.3 m thick interval assigned to Pa. delicatula including Palmatolepis bogartensis, Pa. klugi and Pa. rhe- platys zone. Various taxa, including Pa. clarki, Pa. tri- nana (samples V2-19, V2-22, V2-24 V2-25). Various poly- angularis, Pa. subperlobata, Pa. ultima, Pa. cf. minuta, gnathids (e.g. Polygnathus webbi) and ancyrodellids (An- icriodids and polygnathids were recovered here. The over- cyrodella curvata) also occur in this interval. The lying interval interpreted as Pa. m. minuta to Pa. crepida linguiformis Zone (sample V2-2) is documented by rare Zone (about 2.4 m thick) yielded various palmatolepids occurrences of Pa. linguiformis along with more frequent such as Pa. subperlobata, Pa. triangularis, Pa. spathula, Pa. bogartensis, Pa. cf. nasuta and polygnathids. The Pa. delicatula postdelicatula, Pa. lobicornis, icriodidis Fr-Fa boundary is situated within a 0.1 to 0.15 m thick in- (e.g. Icriodus a. alernatus, I. a. helmsi) and polygnathids terval between samples V2-27 and V2-26 (brachiopod co- (e.g. Po. brevilaminus, Po. webbi). The uppermost part of

262 TomᚠWeiner et al. • An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval

Hády section

Figure 4. Lithology, microfacies, conodont and foraminifer biostratigraphy of the Hády section. Abbreviations: Ca – calcarenite, Cl – calcilutite, Cr – calcirudite Cs – calcisiltite, F – fine-grained, M – medium-grained, C – coarse-grained. Designations HL2-xx (e.g. HL2-11) represent selected cono- dont and thin-section samples. the succession (around 1 m thick) above Pa. minuta minuta (I. alternatus alternatus, I. a. helmsi), ancyrodellids to Pa. crepida Zone thus corresponds to the same or younger (Ancyrodella curvata) and ancyrognathids (e.g. Ancyro- zone. gnathus triangularis). The upper part (about 4.5 m thick) The lowermost part of the Hády section (about 1.6 m was assigned to the Upper rhenana to linguiformis zones. thick) (Fig. 4) yielded relatively poor conodont material This interval yielded various conodonts, including (sample HL2-16), which allowed us to identify the Upper palmatolepids Pa. bogartensis, Pa. rhenana, Pa. nasuta, rhenana Zone (or older). The overlying interval (about Pa. g. extensa, Pa. hassi, Pa. klugi, Pa. cf. linguiformis, 0.8 m thick) supposedly represents the rhenana to polygnathids (e.g. Po. webbi, Po. brevilaminus, linguiformis Zone interval. Palmatolepis linguiformis was Po. aequalis), Ancyrognathus sp. and Ancyroides leonis. not recorded in this section, probably because of its rare occurrence in the studied area and even on a worldwide scale in shallower-water facies. Other palmatolepids from Foraminiferal biostratigraphy this interval include Pa. rhenana, Pa. cf. nasuta, Pa. cf. subrecta, polygnathids (e.g. Po. decorosus, Po. cf. webbi, In all the studied Moravian sections the uppermost Frasn- Po. cf. brevilaminus), Ancyrodella curvata and Ancyroides ian Eonodosaria evlanensis Zone was distinguished. The leonis. It is followed by an interval (0.4 m thick) lacking typical associations of multilocular foraminifers are repre- stratigraphically significant conodonts and typical sented by species of Nanicella, Eonodosaria, Frondilina Frasnian foraminiferal guides, inferred as Pa. sub- and Tikhinella, which are accompanied by unilocular fora- perlobata to Pa. delicatula platys Zone. The entry minifers represented by species of Bisphaera, Irregulla- of Pa. clarki indicated the Pa. delicatula platys Zone. Vari- rina, Parastegnammina and Parathurammina (Hladil et al. ous polygnathids (e.g. Po. aequalis, Po. cf. xylus) were also 1991, Hladil & Kalvoda 1993b, Kalvoda 2002). The asso- found within this interval. The uppermost part of the sec- ciations in the lower parts of the Lesní lom and Šumbera tion (about 1.8 m thick) thus corresponds to the sections (Figs 3, 5) are accompanied by Multiseptida co- Pa. delicatula platys or younger conodont zones, as sug- rallina which indicates the lower part of the Eonodosaria gested by the biostratigraphy of the underlying interval. evlanensis Zone (Kalvoda 2002). However, the vertical The Lesní lom section (Fig. 5) is represented by septation of chambers that enables the distinction between a 22 m-thick Frasnian succession. The lower and middle Multiseptida and Eogeinitzina is often poorly preserved or part of the section (about 18 m thick) is tentatively attrib- destroyed by diagenesis, which makes it difficult to fix the uted to the Upper rhenana (or older) conodont Zone. This last occurrence of Multiseptida. interval yielded various palmatolepids (e.g. Pa. cf. gigas The uppermost Frasnian association of Eonodosaria, gigas, Pa. cf. juntianensis, Pa. bogartensis), polygnathids Eogeinitzina, Nanicella and Frondilina provides reliable (e.g. Po. webbi, Po. politus, Po. cf. brevis), icriodids evidence for the distinction of the Fr-Fa boundary at all

263 Bulletin of Geosciences • Vol. 92, 2, 2017 studied sections (Figs 3–5). The very top of the In the Lesní lom section, the microfacies A is present in linguiformis conodont Zone in the Šumbera section (Fig. 3) the middle and upper part of the section (Fig. 5). marks the last occurrence of the above described Allochems include: unidentifiable mollusc fragments, foraminiferal association indicating that it probably dis- ostracods, crinoids, foraminifers, microproblematics, appeared within the UKWI below or at the Fr-Fa boundary. calcispheres, girvanellid filaments, Rothpletzella, brachio- Foraminifers recorded in the lowermost Famennian are pods, moravamminids, gastropods, peloids, bryozoans and rare and represented by uniloculars, such as Bisphaera sp., trilobites. Some crinoids show bioerosion and/or micrite Irregullarina sp., Eotuberitina sp., Parastegnammina sp. envelopes. Peloids are relatively common. Locally present and Parathurammina sp., which correlate with the “clotted” structure suggests the microbial origin of the Eonodosaria evlanensis–Quasiendothyra communis Inter- microfacies. Locally present cracks in microbialites were zone defined by Kalvoda (2002). infilled by younger microbialites. Some samples from the uppermost part (Upper rhenana to linguiformis zones) of the Lesní lom section contain common sponge spicules Facies and microfacies (LLB 0, LLB 0,25, LLB 1,3). The sample NLL 16,5 is characterized by the common presence of large corals. A) Mudstones and wacke/packstones/microbial boundsto- nes (Fig. 6A, B). – The macroscopic lithology generally B) Peloidal/intraclastic/bioclastic packstones to grainsto- corresponds to calcisiltites to fine-grained calcarenites. nes (locally with transitions to rudstones) (Fig. 6C, D). – Microscopic observation revealed transitions between Based on macroscopic observation, this microfacies cor- mudstones and wackestones to packstones, locally with responds to massive calcarenites. Microscopically, pack- a “clotted” structure. stones to grainstones with somewhat variable content of In the Frasnian part of the Šumbera section, the large peloids, intraclasts and bioclasts were observed. The origin intraclasts of the B and C microfacies (see below) are com- of peloids and the differentiation between peloids and posed of sediment developed as microfacies A. The similar-sized intraclasts is often problematic. In some microfacies was also observed in several restricted strati- cases the peloids are represented by abundant micritized graphic intervals in the Famennian part of the Šumbera sec- renalcids. The blocky sparite prevails, whereas radiaxial tion (samples V2-21, V2-23, V2-3). In these intervals, the fibrous sparite is infrequently present. The fragmentation microfacies are locally finely laminated. Very thin (com- of bioclasts and locally developed grading probably reflect monly less than 1 mm) discontinuous intercalations of the deposition above the storm wave base. peloidal/intraclastic grainstones (B) were locally observed In the Šumbera section, the microfacies locally show (sample V2-23). Bioclasts are mainly represented by crinoid normal or inverse grading in micro-scale. Skeletal ossicles, brachiopods, ostracods and girvanellid filaments. allochems, mainly represented by brachiopods and In places, current-aligned straight-shelled cephalopod shells echinoderms, are relatively rare, with the exception of sev- were macroscopically observed (sample V2-23). eral parts, which are enriched in biota. Brachiopods are Microfacies observed in places are very similar to “clotted” often fragmented; complete articulated shells are rare. structures described by Adachi et al. (2004), Hips & Haas Echinoderms are represented by fragmented or (2006) or Shen & Webb (2008) and can be thus regarded as unfragmented crinoid ossicles, sometimes affected by microbial boundstones. They are commonly rather blurry bioerosion and micritization (micrite envelopes). Other and are more clearly developed in protected areas of the biota include renalcids, isolated girvanellid filaments, microfacies (e.g. under bioclasts or inside of shells). foraminifers, ostracods, conodonts, gastropods and various Intraclastic material of this microfacies A observed in microproblematics. In rare instances, brachiopods form the microfacies B (peloidal/intraclastic/bioclastic pack- nuclei of oncoids (Fig. 6D). The oncoid cortexes consist of stones to grainstones) contains bioclasts, such as girvanellids, Allonema and Rothpletzella. “Clotted” struc- echinoderms, ostracods, girvanellids and peloids. ture is locally present in packstone areas, which suggest a In the Hády section, the microfacies A was observed in microbial origin. Intraclasts, mm- to cm-sized, occur prin- thin-section in the uppermost Frasnian (in intraclastic ma- cipally in the Frasnian part of the section. These intraclasts terial), close to the Fr-Fa boundary (sample HL2-12). Here, are composed of the microfacies A (see above) with locally allochems are composed of crinoids, moravamminids, developed “clotted” strucuture (A). Locally, it is possible peloids, ostracods, foraminifers, microproblematics and to classify the larger intraclasts as reworked microbial girvanellids. The “clotted” structure is locally present, re- boundstones. flecting the microbial origin (microbial boundstone). The In the Hády section, the microfacies B is less common microfacies is common in intraclasts of the microfacies C in the lower part of the section corresponding to the Upper (intraclast rudstones) in various stratigraphic levels across rhenana or older conodont Zone (samples HL2-15, the section. HL2-16). Bioclasts are represented by: crinoids, peloids,

264 TomᚠWeiner et al. • An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval

Lesní lom section

Figure 5. Lithology, microfacies and conodont biostratigraphy of the Lesní lom section. The entire succession corresponds to the Eonodosaria evlanensis foraminifer Zone. Abbreviations: Ca – calcarenite, Cl – calcilutite, Cs – calcisiltite, F – fine-grained, M – medium-grained, C – coarse-grained. Designations “NLL xx” and “LLB xx” (e.g. LLB 2,1 or NLL 12,5) represent selected conodont and thin-section samples. foraminifers, microproblematics, calcispheres, ostracods, type of this microfacies locally contains relatively abun- renalcids, moravamminids and corals. dant udoteacean algae (sample V2-19). Stromatactis was The microfacies B is dominant, especially in the lower locally observed. Some peloids are obviously strongly part, while it is also present in the middle part of the Lesní micritized renalcids. lom section. Skeletal debris is mostly represented by In the Hády section, the rudstones are present across the echinoderms, moravamminids and, locally, mollusc frag- entire succession. Bioclasts are represented by: brachio- ments. Unlike the Šumbera and Hády sections, this pods, corals, gastropods, foraminifers, calcispheres, micro- microfacies often contains large corals in Lesní lom. Other problematics, ostracods, conodonts and ichthyoliths. bioclasts include: ostracods, brachiopods, foraminifers, Intraclasts are mainly represented by “clotted” wacke/pack- stromatoporoids, microproblematics, bryozoans, girvanellids stones of the microfacies A with various bioclasts (e.g. and moravamminids, some of them with micritic envelopes. echinoderms, brachiopods, moravamminids, calcispheres, ostracods) and, partly by peloidal/intraclast grainstones. C) Intraclast rudstones (Fig. 6E, F). – This microfacies Stromatactis structures are abundant in higher parts of the macroscopically corresponds to limestone breccias (calci- section. rudites). Microscopic observation revealed large intraclasts In the Lesní lom section, the intraclast/peloidal surrounded by pack- to grainstone-matrix composed of rudstone was only observed in the sample NLL 12,5. microfacies B (peloidal/intraclastic/bioclastic packstones Allochems are represented by ostracods, brachiopods, to grainstones). The large cm-sized intraclasts, composed gastropods and peloids. Large intraclasts are represented of the microfacies A, are often elongated and angular to by mudstones, wacke/packstones and microbial bound- subangular, suggesting very short transport. Normal and stones with a “clotted” structure of the microfacies A. inverse grading was locally observed. Biota in the intraclastic material include ostracods, gastro- In the Šumbera section, intraclast rudstones occur, pods, calcispheres, foraminifers and Rothpletzella. especially in the Frasnian part. Skeletal allochems are rep- resented by fragmented echinoderms (crinoids), brachio- D) Brachiopod rudstone (Fig. 6G, H). – This microfacies pods, girvanellids, moravamminids, foraminifers, tabulate is restricted to a single bed approximately 5 cm thick at and rugose corals, udoteacean and solenoporacean algae, the Šumbera section (sample V2N4, assumed as Lower bryozoans, Rothpletzella and ichthyoliths. A specific sub- triangularis Conodont Zone). It is characterized by large

265 Bulletin of Geosciences • Vol. 92, 2, 2017 articulated and fragmented brachiopods surrounded by Trench section) to almost 1 m (Aeke Valley) (compare e.g. blocky and radiaxial fibrous sparite and spaces infilled Schindler 1988, 1990b, 1993; Gereke & Schindler 2012). by intraclast/peloidal grainstones (microfacies B). Large Deposition of intraclastic rudstones in Šumbera and complete brachiopod shells are often filled with cement or particularly Hády sections and occurrence of Frasnian con- peloidal/intraclastic grainstone with fragmented brachio- tinental basal clastics in the near vicinity (Štelcl 1969, pods and echinoderms. Blocky and radiaxial fibrous spa- Krmíček 2006) suggest rather shallower environment pos- rite cements were also observed in some brachiopod infills. sibly in the proximal part of a carbonate ramp. The Lesní The fragmentation and chaotic arrangement of brachio- lom section is generally characterized by thicker and more pods suggests hydrodynamic transport possibly during fine-grained sediments (mudstones to grainstones), which a storm event. probably reflect a relatively more distal position to the shore than in the case of Šumbera and Hády sections. The basic differences between the pelagic limestones in Environmental comparison of Steinbruch the Steinbruch Schmidt section and the limestones of the Schmidt and Moravian Karst sections Moravian Karst deposited on a wide carbonate ramp are mainly recognisable in respect to the fossil content and the Combined observations of sedimentology/facies and fos- sedimentary features. Whereas in the Kellerwald area fos- sil content show that the Steinbruch Schmidt succession sils of the pelagic offshore realm dominate (e.g. has been deposited in significantly deeper water than the dacryoconarids, homoctenids, goniatites, straight-shelled sediments from the Moravian Karst sections. In Stein- cephalopods, entomozoacean ostracods), the Moravian bruch Schmidt barely any intraclasts, no coquinas of ben- Karst sections yield a variety of shallow-water organisms thic organisms and no stromatactis features are present. (e.g. brachiopods, bryozoans, benthic foraminifers, corals, However, hardgrounds are developed in some of the beds crinoids, trilobites as well as different kinds of algae); (e.g. in the marker bed below the UKWI – see Schindler peloids, bioeroded shells and coquinas of fragmented 1993, Gereke & Schindler 2012) and intense bioturbation shells are also present. The prevailing carbonates in the is present. Steinbruch Schmidt section are mud- and wackestones The rocks of the Steinbruch Schmidt section were de- whereas in the Moravian Karst grainstones, packstones, posited on a submarine rise surrounded by relatively rudstones and even breccias are frequent. In summary, deeper basinal areas (e.g. Schmidt 1925, 1935; Rabien there is a low-energy deeper-water facies in the Steinbruch 1956; Meischner 1971) whereas the Moravian Karst sec- Schmidt section and successions of high-energy shal- tions were deposited in a carbonate ramp environment low-water facies in the Moravian Karst. (Hladil 1991). The Steinbruch Schmidt section belongs to the Rhenohercynian Belt and comprises cephalopod lime- stone facies (e.g. Tucker 1974, Tucker & Wright 1990). Gamma-ray spectrometry The cephalopod limestones – as well as the embedded Kellwasser intervals – are often very condensed. For the The basic statistics of the measured gamma-ray values are Kellwasser intervals this reduced thickness can be ob- presented in Tab. 1 and all measured values are in Table I in served e.g. in the Kellwasser type locality in the Kellwasser the electronic supplementary appendix. The CGR values Valley of the Harz Mountains (e.g. Gereke & Schindler vary from 0.8 to 49.8 API. Relatively high values were meas- 2012, Gereke et al. 2014) or in the Sessacker Trench sec- ured in the pelagic limestones of the Steinbruch Schmidt tion in the Dill Syncline of the Rheinisches Schiefergebirge section, whereas much lower values are typical for sections (e.g. Schindler et al. 1998). The thickness of the in the Moravian Karst (Fig. 7; Tab. 1). The highest covari- Kellwasser sediments may vary significantly, from one ance with the total dose rate was found for K (R2 = 0.82) in bed of 0.1 to 0.2 m (e.g. Hühnerbach Valley, Sessacker Steinbruch Schmidt. This suggests that K mainly drives the

Figure 6. Thin-section microphotographs (A–D, F, H) and photographs of polished slabs (E, G) illustrating representative examples of the microfacies described in the text. • A, B – microfacies A; A – mudstone to wackestone with blurry “clotted” structure, larger cephalopod and fragmented bioclasts are present, Šumbera section (sample V2-23); B – burrowed wackestone with fragmented bioclasts, Lesní lom section (sample LLB 2,1). • C, D – microfacies B; C – laminated peloidal/intraclastic packstone to grainstone, Šumbera section (sample V2-7); D – peloidal/intraclast/bioclastic grainstone to rudstone with oncoids, Šumbera section (sample V2-19). • E, F – microfacies C; E – rudstone with large intraclasts, Šumbera section (sample V2-27); F – intraclast rudstone (microfacies C) composed of “clotted” microbial mudstone or wackestone intraclasts (microfacies A) surrounded by intra- clast/peloidal/bioclastic grainstone (generally corresponding to microfacies B), Hády section (sample HL2-11). • G–H microfacies D; G – accumulation of large brachiopods, Šumbera section (sample V2-26/V2N4); H – brachiopods with infills of intraclast/peloidal grainstone or blocky and radiaxial fi- brous cement, Šumbera section (samples V2-26/V2N4). • Scale bars for A–D, F, H ~ 5 mm; scale bars for E, G ~ 10 mm.

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A B

C D

E F

G H

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Table 1. Calibration equations used for conversion of XRF signal (cps) two horizons can be correlated with LKWI and UKWI to ICP-MS oxide and element concentrations (wt%, ppm). from the Steinbruch Schmidt (Fig. 8). Oxide/element Calibration equation R2

SiO2 SiO2 (wt%) = 0.0002 × Si (cps) + 0.0771 0.990 Bulk magnetic susceptibility Al2O3 Al2O3 (wt%) = 0.0002 × Al (cps) + 0.2671 0.991 CaO CaO (wt%) = 0.0001 × Ca (cps) + 3.0784 0.998 Fe O Fe O (wt%) = 0.0001 × Fe (cps) + 0.0348 0.994 Median MS values for each section are reported in Tab. 2 2 3 2 3 and all measured values are in Table II in the electronic K OKO (wt%) = 0.0001 × K (cps) + 0.1664 0.996 2 2 supplementary appendix. Samples from the Steinbruch TiO2 TiO2 (wt%) = 0.0001 × Ti (cps) – 0.0298 0.992 Schmidt have the highest values; the Hády and Šumbera MnO MnO (ppm) = 0.0001 × Mn (cps) – 0.0056 0.993 sections have lower values and the lowermost mean values Rb Rb (ppm) = 0.9707 × Rb (cps) – 0.311 0.999 come from the Lesní lom section. Our MS curve of the Sr Sr (ppm) = 1.2185 × Sr (cps) – 12.171 0.996 Steinbruch Schmidt section corresponds in high detail with Zr Zr (ppm) = 1.1708 × Zr (cps) – 4.8282 0.997 the MS curves published by Crick et al. (2002) and Riquier Cu Cu (ppm) = 0.7812 × Cu (cps) – 5.1203 0.983 et al. (2009; correlation is less straightforward due to lower Pb Pb (ppm) = 0.9996 × Pb (cps) – 2.7427 0.999 number of samples), which illustrates a good reproducibi- Zn Zn (ppm) = 0.8444 × Zn (cps) – 5.7096 0.989 lity of the MS data. MS is generally high in the interval from the base of the section (Lower rhenana conodont Zone) to the upper part of the Upper rhenana conodont gamma-ray signal, which is usually contained in detritic Zone (1 m above LKWI) (Fig. 7). MS within the LKWI is components, such as clay minerals, micas and K-feldspars highly variable, ranging from very high to very low values (Rider 1999, Doveton & Meriam 2004). The second impor- (both in shale and limestone beds). Upper parts of the tant source of the gamma-ray signal in the Steinbruch Upper rhenana and the lower portions of the linguiformis Schmidt is uranium (dose rate vs. U: R2 = 0.75), which is conodont zones are characterized by lower values, which usually carried by detritic heavy minerals, authigenic phos- again increase at the base of the UKWI. Maximum MS phates and organic matter (Rider 1999, Doveton & Meriam values are observed within and just above the UKWI. In 2004, Lüning et al. 2004). The LKWI and UKWI are cha- general, MS is relatively high in the Famennian and dis- racterized by higher CGR, U and U/Th values (U/Th 0.6 in plays two cycles (Fig. 7). the LKWI; 0.85 in the UKWI) in the Steinbruch Schmidt. The MS curve of the Hády section shows several corre- U/Th values vary between low values (0–0.74) in nodular lative features with the Steinbruch Schmidt curve. Two limestones and relatively higher values (0.75–0.85) in the levels with increased MS values occur just below the Fr-Fa LKWI and UKWI (Fig. 7), which are indicative of oxic and boundary (Upper rhenana to linguiformis conodont zones) hypoxic conditions, respectively (e.g. Jones & Manning corresponding to the GRS-based equivalents of the LKWI 1994, Marynowski et al. 2012, Rakociński et al. 2016). and UKWI (Fig. 7). There is no distinct MS record in the Values continue to be relatively high up to the “post-event” Kellwasser Crisis interval in the Lesní lom and Šumbera intervals while a second weaker U and CGR peak, related to sections, although the uppermost Frasnian parts have gen- thin shaly intercalations, occurs above both event intervals. erally higher values compared to the underlying succession In the Moravian Karst, U has the highest statistical cor- (Fig. 7). MS values markedly increase in the upper part of relation with total dose rate (R2 = 0.78–0.98) as compared the Famennian at the Hády (from Palmatolepis delicatula with K and Th (Tab. 2). In general, U/Th values are high platys or higher conodont zones) and Šumbera section (0.8–12.7) in the Moravian Karst sections, owing to the (Pa. minuta minuta or younger zone). relatively low Th and relatively high U concentrations (Tab. 2; Fig. 7). An interval with two peaks of U concentra- tions and relatively high CGR values occurs in the upper- Element geochemistry most Frasnian limestones (Upper rhenana to linguiformis biozones) at the Lesní lom and Hády sections. Based on the Median values of major and trace element concentrations biostratigraphic position and the gamma-ray signal these for each section are listed in Tab. 3 and all measured values

Figure 7. Key curves of petrophysical (CGR, U, U/Th, MS) and geochemical (SiO2, Rb, TiO2, CaO, Zr/Rb, Pb, Fe2O3) proxies from the studied Rheinisches Schiefergebirge (Steinbruch Schmidt) and Moravian Karst (Hády, Šumbera, Lesní lom) sections. Conodont zones in Steinbruch Schmidt after Feist & Schindler (1994); *bed numbers from Schindler (1990). < LOD = below limit of detection. Abbreviations: rhe – rhenana, lin – linguiformis, su – Pa. subperlobata, tr – Pa. triangularis, pl – Pa. delicatula platys, min – Pa. minuta minuta, crepida – Pa. crepida, L – lower, U – Upper, St. – stage, C.z. – Conodont zone, M. – metres, S. – sub-section of composite section; UGRS – gamma-ray measured U, UICP – ICP-MS measured U.

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Figure 8. Correlation of the studied Moravian Karst and Rheinisches Schiefergebirge Fr-Fa sections based on the conodont biostratigraphy and U gamma-ray, magnetic susceptibility, SiO2 and Zr/Rb logs. Correlative trends of the Zr/Rb curves are marked by arrows.

Table 2. Median (med), minima (min) and maxima (max) of gamma-ray spectrometry and magnetic susceptibility values and covariance between total dose rate (TOT) and U, K and Th for each of the studied sections. CGR K U Th U/Th TOT:U TOT:K TOT:Th Th/K MS units API % ppm ppm R2 R2 R2 R2 min 28.1 0.8 0.5 3.4 0.1 4.21·10-8 Steinbruch Schmidt (n = 45) med 34.9 1.1 1.0 4.4 0.2 0.8 0.8 0.3 0.4 1.67·10-7 max 49.8 1.8 3.9 6.0 0.8 3.9·10-7 min 12.8 0.4 2.6 1.5 1.0 6.25·10-10 Hády (n = 42) med 21.8 0.7 4.8 2.5 2.1 0.9 0.4 0.5 0.7 5.76·10-8 max 35.3 1.2 10.1 4.0 3.0 2.98·10-7 min 6.8 0.1 2.0 0.9 0.3 –3·10-8 Šumbera (n = 56) med 14.3 0.4 3.6 2.2 0.6 0.8 0.3 0.4 0.4 5.17·10-8 max 23.1 0.5 5.4 3.8 1.3 4.92·10-7 min 0.8 0.0 0.9 0.2 1.1 –6.7·10-8 Lesní lom (n = 48) med 5.4 0.1 3.2 0.8 4.4 1.0 0.4 0.3 0.4 3.92·10-8 max 12.4 0.4 7.2 1.9 12.7 1.41·10-7

Table 3. Median values of selected oxides and elements measured by XRF and calibrated by independent ICP-MS analysis. *SiO2 and K2O concentra- tions are below detection limits in prevailing number of samples from the Moravian Karst and the median was calculated just from few samples with de- tectable (considerably higher) values.

Sections Al2O3 SiO2 K2O TiO2 CaO Fe2O3 MnO Zr Rb Sr Pb Zn wt% ppm Steinbruch Schmidt (n = 147) 2.3 6.5 0.5 0.1 41.0 0.5 0.1 39.3 16.6 248.3 5 8.7 Hády (n = 146) 0.7* 0.7 0.2* 0.01 45.4 0.1 0.01 2.2 2.0 286.1 0.7 5.4 Šumbera (n = 162) 0.5* 0.6 0.2* 0.01 45.2 0.1 0.01 2.3 2.0 233.5 1.1 5.5 Lesní lom (n = 144) 0.6* 0.8 0.2* 0.01 45.7 0.1 0.01 3.9 2.7 204.7 4.0 6.2

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A

B

Figure 9. A – principal component analysis of the XRF data from the studied sections.•B–bivariate plots of the magnetic susceptibility and XRF mea- sured non-calibrated Rb and Fe values (cps units) from the Hády section. Statistical correlation is very poor between MS and Rb or Fe in other studied sec- tions. are in Table III in the electronic supplementary appendix. considered a conservative proxy of clay-sized detrital Median concentrations of measured elements markedly fractions in sediments (e.g. Schulte & Speijer 2009, Jones differ between the Moravian Karst sections and Steinbruch et al. 2012). Normalizations to Rb or Al are used to elimi- Schmidt (Tab. 3). The concentrations of typically terrigen- nate the dilution effect of quartz and carbonate minerals ous detrital elements, such as Al, K, Ti, Zr and Rb are about due to variable grain size and rate of carbonate production two- to one-order of magnitude lower in the pure in marine depositional settings (e.g. Brumsack 2006), al- shallow-marine limestone facies from the Moravian Karst though pitfalls are related to this approach (see Van der as compared with the deeper-marine nodular and black Weijden 2002). limestones, marlstones and shales from Steinbruch Principal Component Analysis (PCA) revealed several Schmidt (see Tab. 3). The Al2O3 concentrations are below groups of elements, which show similar geochemical affin- the detection limits (DL) of the XRF device in the prevail- ities and behaviour in our XRF dataset (Fig. 9a). Group 1 ing number of samples (Lesní lom: 107 samples < DL/44 represents elements usually related to detrital terrigenous samples > DL; Hády 63/23; Šumbera 95/11) from the Mo- fraction in sediments, Al, Si, K, Ti, Zr and Rb, both for the ravian Karst; therefore they were applied in normalisation Moravian Karst sections and Steinbruch Schmidt (Fralick only when the measured data made it possible. Consequent- & Kronberg 1997, Rachold & Brumsack 2001, Niebuhr ly, the target element concentrations were normalised to 2005, Sageman & Lyons 2005, Śliwiński et al. 2010, Rb, which is an alternative refractory terrigenous element Whalen et al. 2015, Bábek et al. 2016). Data from the

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Moravian Karst revealed good statistic correlation between tween the two KWI (Schindler 1990b, 1993; Kaufmann et Rb, Si and Zr (R2 = 0.7–0.9) and a markedly lower correla- al. 2004). tion between Ti and Si, Rb, Zr (R2 = 0.2–0.4; Fig. 9a). Alu- Based on a combination of the above-mentioned geo- minium measured in a few samples with an Al content chemical signatures (Al increase, Zr/Rb, Ti/Rb decrease in above detection limits revealed good statistic correlations KWI) and biostratigraphy, the Moravian Karst sections can (R2 = 0.8–0.9) with Si, Rb and Zr. High negative correla- be correlated in high-resolution manner with the Stein- tion (R2 = –0.5 to –0.8) between these detrital proxies and bruch Schmidt (Fig. 8). These correlations are consistent the carbonate proxy Ca (Fig. 9a) reflects the effect of dilu- with GRS and MS correlations. tion of terrigenous siliciclastics in marine carbonates Good correlations of Fe vs. Si (R2 = 0.8–0.9) and Fe vs. (Brumsack 2006). The concentrations of Al, Si, K, Ti, Zr Rb (R2 = 0.7–0.8; Fig. 9b) at Hády and Šumbera suggest and Rb increase and the Zr/Rb and Ti/Rb ratios decrease in that most of Fe is associated with the clay fraction. These the equivalents of the KWI in the Moravian Karst sections, correlations are lower (R2 = 0.3–0.4) in Steinbruch along with the increasing MS values and UGRS concentra- Schmidt and Lesní lom. MS and the detrital proxy curves tions (Fig. 7). As Zr and Ti are contained in silt- and reveal very similar stratigraphic trends (Fig. 7). Moreover, fine-grained sand-sized heavy minerals, the Zr/Rb and data from the Hády section show a high statistic correlation Ti/Rb ratios can be used as proxies of detrital grain size in between MS vs. Rb (R2 = 0.8; Fig. 9b), MS vs. Si (R2 = 0.8) fine-grained siliciclastic and mixed carbonate-siliciclastic and lower correlation between MS vs. Ti (R2 = 0.4). This sediments (e.g. Fralick & Kronberg 1997, Dypvik & Harris suggests that the MS signal from the studied sections is 2001, Schulte & Speijer 2009, Jones et al. 2012, Nováková driven by detrital particles diluted in the diamagnetic cal- et al. 2013). This geochemical signature suggests that car- cium carbonate (see Riquier et al. 2009 for comprehensive bonate production decelerated during the KWE along with MS analysis of the Steinbruch Schmidt section). the decreasing grain size of the detrital supply. On the other Group 2 from the PCA comprises of elements Pb, Cu hand, Zr/Al2O3 can be used as a proxy of volcanic input and Zn in Steinbruch Schmidt (Fig. 9a) and Pb and Cu in (Racki et al. 2002, Yudina et al. 2002, Pujol et al. 2006). the Moravian Karst sections, which are often used as Sufficiently high Al concentrations (above detection limits) palaeoproductivity and redox potential proxies (e.g. were measured from the LKWI and UKWI and the basal Schnetger et al. 2000, Dean 2007, Śliwiński et al. 2010). In Famennian strata, suggesting that the Zr/Al2O3 ratio could all Moravian sections, Cu, Pb and partly Zn show poor cor- be used for comparative purposes. The Zr/Al2O3 values are relation with the other elements. Zn correlates well with Rb higher than 0.001 (mean values 0.003) suggesting a volca- in the basal Famennian strata at Šumbera and Hády sec- nic input, as reported by Racki et al. (2002), in a geographi- tions (R2 = 0.7), reflecting its association with clays cally close section in southern Poland. In addition, a re- (Schlegel et al. 2001, Sdiri et al. 2014). In the Lesní lom markable excess of Ti in the Moravian Karst Fr-Fa sections section, high values of Pb were found in the UKWI and (mean Ti/Al = 0.2), relative to the Post Archean Australian correlate partly with high Rb (Fig. 7). Lead weakly correl- Shale (PAAS) standard (Ti/Al = 0.06; Taylor & McLennan ates with Fe (R2 = 0.3) at Lesní lom, which may indicate its 1985), suggests that Ti may be connected with Ti rich incorporation in pyrite. Nevertheless, higher contents of Pb mafic volcanism (Dvořák 1985, Přichystal 1993, Janoušek may also be attributed to microbialites (Kamber et al. et al. 2014). 2004). In the Steinbruch Schmidt, there is a very good correla- Zinc and lead show good statistic correlation (R2 = 0.8) tion (R2 = 0.9) between all the measured detrital proxies in the Steinbruch Schmidt, whereas correlation between (Group 1; Si, Al, Ti, K, Rb, Zr; Fig. 9a) and a very high Cu/Zn and Pb/Cu is poor (R2 = 0.1–0.2). Aluminium and negative correlation of the detrital proxies with Ca (R2 = Rb moderately correlate with Cu (R2 = 0.6) but weakly –0.9). The concentrations of detrital proxies increase in the with Pb and Zn (R2 = 0.2). Zinc and Cu reveal very low cor- shales of the KWI and in the basal Famennian strata, whilst relation with Fe (R2 = 0.2–0.3). These correlations may in- Zr/Rb, Zr/Al, Ti/Rb and Ti/Al decrease in the KWI. The dicate that a significant portion of Cu is incorporated in Zr/Al and Zr/Rb values, which have both the same trends clay minerals and Pb and Zn probably in organic matter. and high covariance (R2 = 0.7), reveal cyclic pattern in the Zinc and Cu are partially related to pyrite. Concentrations Steinbruch Schmidt: a decrease toward the LKWI base fol- of non-normalised palaeoproductivity proxies Pb (Fig. 8), lowed by increase to the base of the linguiformis Zone and, Zn and Cu, as well as Pb/Rb, Zn/Rb and Cu/Rb increase in again, a decrease toward the base of the UKWI and in- the LKWI and more distinctively at the top of the UKWI. crease toward the Upper triangularis (= Pa. minuta Ratios of Mn/Al and Fe/Al are often regarded as prox- minuta) conodont Zone. The Zr/Al2O3 ratios suggest a pos- ies of hydrothermal input (Taylor & McLennan 1985) or sible derivation of the detrital phase from volcanic sources anoxic conditions (Maynard 2005, Lyons & Severmann in the Steinbruch Schmidt (mean values 0.0018), which 2006). In the Moravian Karst, anomalously high Mn/Al may be supported by the occurrence of a bentonite layer be- ratios (mean 0.146; compare to PAAS: Mn/Al = 0.0085)

272 TomᚠWeiner et al. • An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval may indicate a general hydrothermal influence connected Before starting a discussion of geochemical and with widespread bimodal magmatism (Přichystal 1993, Ja- petrophysical signatures it is important to highlight that the noušek et al. 2014). Manganese does not correlate with Fe, limestones in Moravia are very pure and were deposited in while higher Fe/Al (mean value 0.9) may reflect anoxic an area, to a certain extent similarly as in the neighbouring conditions (Lyons & Severmann 2006) or could be also southern Poland, under the influence of strong bimodal linked to volcanic activity. magmatism (Přichystal 1993, Racki et al. 2002, Kalvoda et Uranium measured by ICP-MS (and calculated U/Th) al. 2008, Janoušek et al. 2014) and that their detrital input shows higher values compared to UGRS in both the KWE may have been largely controlled by atmospheric volcanic black shale intervals from Steinbruch Schmidt (Fig. 7). transport. Lower values of U/ThGRS are caused by the averaging of U Carbonate successions of the Moravian Karst display and Th content in a larger bulk of scanned rock, which in- an increase in detrital proxies (Al, K, Si, Rb, Zr and Ti con- cluded surrounding limestones. tents), GRS measured U concentrations, U/Th ratios and MS values in the uppermost Frasnian (Upper rhenana to linguiformis conodont zones) strata. In contrast the Zr/Rb, Discussion Ti/Rb ratios and CaO content decrease (Figs 7, 8). These geochemical trends correlate with the Kellwasser intervals The conodont biostratigraphic data from the Moravian sec- in the reference section of Steinbruch Schmidt, where high tions document the overall biostratigraphic span of the detrital concentrations are present in the shaly beds and low Lower or Upper rhenana to Palmatolepis minuta minuta or concentrations in limestones of KWE; whereas Zr/Rb and younger conodont zones and enable to us follow the biotic Ti/Rb values are low and U/Th values are high both in and facies changes at the Fr-Fa boundary in detail. Multilo- shaly and carbonate facies of KWE (Figs 7, 8). A decrease cular foraminifers of the Eogeinitzina, Eonodosaria- in Ti/Rb and Zr/Rb in the KWE level in the Moravian Karst Nanicella association reach the UKWI and disappear at or and Steinbruch Schmidt section is in accordance with data below the Fr-Fa boundary. The Moravian facies are repre- from the Harz Mountains and in the LKE level from the sented by ramp limestones (see Hladil et al. 1991). The Eifel Mountains in Germany (Pujol et al. 2006, Riquier et metazoan reef environment was considerably reduced dur- al. 2006). Contrary to Dopieralska et al. (2016) who based ing the late Frasnian (Schindler 1990b, McGhee 1996, on Nd isotopes (among others also in Steinbruch Schmidt Copper 2002). Heavily calcifying biota was largely repla- section) postulated a fall in sea level during the deposition ced by calcimicrobial consortia, such as Renalcis, Roth- of the Kellwasser intervals, the decrease in Ti/Al was inter- pletzella, Girvanella and Epiphyton, which dominated in preted here as the result of restricted clastic input during the uppermost Frasnian and Famennian (Copper 2002). sea-level rise (Pujol et al. 2006, Riquier et al. 2006). The Microbial facies reflecting this environmental change were decrease in grain size of the siliciclastic supply and carbon- recorded from various shallow-water settings across the ate productivity in the KWE intervals is as a consequence world (e.g. Wood 2000, Whalen et al. 2002, Chow & George of a deepening and is in accord with our geochemical sig- 2004, Shen et al. 2008, Rakociński & Racki 2016) al- nature from the Moravian Karst and the Steinbruch though the traces of microbial activity were also recorded Schmidt sections. The minima in Zr/Rb at the base of the in deep-water environments (eg.in the Holy Cross Moun- LKWI and UKWI in Steinbruch Schmidt coincide with the tains; Marynowski et al. 2011). Microbial structures repre- maximum flooding surfaces reported by Devleeschouwer sented by renalcids and Rothpletzella from the Šumbera et al. (2002). The Zr/Rb increase is related to prograd- area were previously depicted by Racki et al. (2002). The ational microfacies parasequences (Devleeschouwer et al. currently recorded Moravian association of calcimicrobes 2002) of highstand system tract (LKWI) and lowstand sys- is more diversified than that found in the Holy Cross Mts. tem tract (above LKWI in the Upper rhenana conodont in Poland (Rakociński & Racki 2016) and might be compared Zone), together with lower parts of a transgressive system with calcimicrobe associations from reef environments at tract (top of the Upper rhenana conodont Zone). Values of various sites, including the Australian Canning Basin Zr/Rb decrease in the upper part of the transgressive sys- (e.g. Wood 2000, 2004), China (Shen et al. 2010) or Rus- tem tract (linguiformis conodont Zone) and reaches a mini- sia (Antoshkina 2006). However, the Moravian Karst mum at the maximum flooding surface at the base of ramp environment was less favourable for the develop- UKWI. Zr/Rb values increase again during the highstand ment of larger mud mounds than those reported from system tract of the UKWI. Australia (e.g. Wood 2000, 2004) or China (Shen et On the other hand, an increase in Zr/Al2O3 was reported al. 2010). Nevertheless, the wide occurrence of micro- from the KWI of the Holy Cross Mountains, Poland, from bial limestones and calcimicrobes in the Moravian Karst the Montagne Noire, France and the Polar Urals, Russia follows the global trends during the uppermost Frasnian (Racki et al. 2002, Yudina et al. 2002, Pujol et al. 2006). and lower Famennian. The increase in Zr/Al2O3 (> 0.001) can be explained by

273 Bulletin of Geosciences • Vol. 92, 2, 2017 a coarser clastic, often volcaniclastic contribution (Racki et noticed a similar anomalously high content of U, displayed al. 2002, Pujol et al. 2006, Racki et al. 2012). Racki et al. by very low Th/U signatures, in the Eifelian and Frasnian (2002) also reported a Zr/Al2O3 increase at the base of the shallow water “pure” limestones of the Moravian Karst. Famennian from probably another Šumbera section, which They excluded the effect of anoxic waters on the U enrich- can be equivalent to a Zr/Rb peak in the Lower triangularis ment due to low total organic carbon (TOC) concentrations (= Pa. subperlobata) conodont Zone from our dataset and low U: TOC covariance; furthermore they reported (Fig. 7). However, this interval was not documented from similar U-rich carbonates from the NE margin of the Great the base of Famennian at Hády. The excessive Zr, showing Bahama Bank, where U is related to impurities from Saha- good correlation with Rb and Si and excessive Ti in the ran dust. Variations in U concentration correlate well with Moravian Karst, together with similar data from southern XRF siliciclastic content in the Lesní lom and Hády sec- Poland, may represent a reflection of the widespread co- tions (Fig. 7). This could indicate that a potential source of eval bimodal magmatism of the Moravian-Silesian Zone U enrichment is the detritic fraction, possibly derived from (Dvořák 1985, Přichystal 1993, Janoušek et al. 2014). It the widespread Devonian felsic volcanites (Gilíková et al. may also be in accord with anomalously high Mn/Al, 2006, Krmíček 2006). However, higher U enrichment may which is a proxy of hydrothermal input. A good statistical also reflect the bias of normalisation in pure limestones. In- correlation exists between Si, Rb and Zr in the Moravian creased U and decreased Th/U were reported previously Karst sections, which may be in accordance with the com- from other Moravian Karst Fr-Fa sections (Ostrov mon presence of zircon of volcanic origin in the Frasnian u Macochy, Mokrá; Bábek et al. 2007) and from the sediments from Moravia (Hladil 2002, Gilíková et al. Hranice Palaeozoic (Czech Republic; Hladil et al. 2006). 2006, Krmíček 2006). Volcaniclastic ilmenite, epidote, zir- The U maxima of LKWI and UKWI from Lesní lom and con and rutile were reported in Devonian tuffites, which Hády (Fig. 8) can be correlated with maxima of the lower were found in close vicinity of the studied sections and upper part of the 6th cycle of Hladil et al. (2006, p. 234). (Gilíková et al. 2006, Krmíček 2006). However, Al (or High U/Th values from the KWI were also reported in earl- Al2O3) normalization could be biased due to very low Al ier studies from Montagne Noire and Morocco (Riquier et concentrations, which can result in artificially higher ratios al. 2005, 2009) and low Th/U values from the Holy Cross (Van der Weijden 2002, Tribovillard et al. 2006, Collin et Mountains, Poland (Bond & Zatoń 2003, Bond et al. 2004) al. 2015). This could also play a role in the case of the and Alberta, Canada (Bond et al. 2013). This is in accor- Moravian sections. dance with interpretation of hypoxic to anoxic conditions In all Moravian sections, Cu, Pb and, to some extent, Zn associated with both KWE maximum flooding surfaces show poor correlation with the other elements and are (Devleeschouwer et al. 2002), based on the high TOC con- probably mostly bound to organic matter. The absence of tent and excessive concentrations of siderophile and mutual correlation among palaeoproductivity proxies in all chalcophile elements (Racki et al. 2002, Tribovillard et al. sections probably reflects their relative affinities to differ- 2004, Riquier et al. 2005, Pujol et al. 2006). Geochemical ent types of organic matter. and sedimentological proxies indicate a widespread The KWI in the Moravian Karst and Steinbruch hypoxia to anoxia typical of most sections exhibiting the Schmidt are characterized by increased U and U/Th. Sea- Kellwasser Crisis (Joachimski & Buggisch 1993, Racki water U is taken up by sediments under suboxic to anoxic 2005, Gereke & Schindler 2012, George et al. 2014); how- conditions (Zheng et al. 2002, Morford et al. 2009), result- ever, exceptions do occur (Carnic Alps, Austria; Bond et ing in enrichment relative to Th (Wignall & Myers 1988). al. 2004). Gereke (2007) discussed the possibility that even However, U is mobile during diagenesis and/or can be tied local oxic “events” may be involved in the course of the to detrital minerals (Calvert & Pedersen 1993, Jones & Kellwasser Crisis. Manning 1994). In pure limestones of the Moravian sec- tions the U content is significantly higher compared with that of the black shales of LKWI and UKWI in Steinbruch Conclusions Schmidt (Tab. 2; Fig. 7). Higher Th concentrations are characteristic of clastic sediments (or clastic-rich carbon- The detailed conodont zonation in the Moravian sections ate sediments) rather than for “pure” carbonates; thus the made it possible to follow, in detail, biotic changes across U/Th ratio can therefore be higher in carbonate sediments the Fr-Fa boundary. The ramp limestones recorded the de- (Bond et al. 2004). However, high U/Th values from the cline of metazoan biota, largely replaced by rich calcimic- Moravian Karst Fr-Fa sections (Fig. 7) are uncommon in robial associations, thus consistent with the global trend sedimentary limestones deposited in oxygenated environ- during this interval. The association of multilocular fora- ments ranging from shallow epeiric seas to deep open minifers reached the UKWI and became extinct in the up- oceans (Plank & Langmuir 1998, Ruffell & Worden 2000, permost Frasnian close to the Fr-Fa boundary. The Kell- Hladil et al. 2006, Bond et al. 2013). Hladil et al. (2006) wasser Crisis left comprehensible petrophysical and

274 TomᚠWeiner et al. • An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval geochemical signatures in the studied Fr-Fa sections from Platform): stratigraphy and sea-level changes. Tectonophysics the Moravian Karst. These were probably related to a de- 268, 149–168. DOI 10.1016/S0040-1951(96)00229-6 crease in carbonate productivity, which caused a relative ALGEO, T.J. & SCHECKLER, S.E. 1998. Terrestrial–marine increase in siliciclastic components in the sediments (Si, teleconnections in the Devonian: links between the evolution Rb, Ti and Zr; Fig. 7). Lower Zr/Rb and Ti/Rb ratios of land plants, weathering processes, and marine anoxic events. Philosophical Transactions of the Royal Society of (Fig. 8) indicate a decrease in grain size, related to the in- London B 353, 113–130. DOI 10.1098/rstb.1998.0195 crease in distance from a clastic source, or attenuation of ALGEO, T.J., BERNER, R.A., MAYNARD, J.B. & SCHECKLER, S.E. aeolian transport. Similar changes were documented from 1995. Late Devonian oceanic anoxic events and biotic crises: the reference section Steinbruch Schmidt, related to maxi- ‘Rooted’ in the evolution of vascular land plants? GSA Today mum flooding surfaces and high stand system tracts (Dev- 5, 64–66. leeschouwer et al. 2002) of both KWI (Fig. 8). Element ANTOSHKINA, A.I. 2006. Palaeoenvironmental implications of normalizations in the Moravian Karst sections may be some- Palaeomicrocodium in Upper Devonian microbial mounds of what biased due to the pure limestones. However, signifi- the Chernyshev Swell, Timan-northern Ural Region. Facies 52, 611–625. DOI 10.1007/s10347-006-0083-z cant Zr, TiO2,MnorFe2O3 enrichments may indicate some influence of volcanic sources at the studied Moravian Karst BÁBEK, O., KALVODA, J., ARETZ, M., COSSEY, P.J., DEVUYST, F.X., Fr-Fa sections, which is in accordance with previous re- HERBIG, H.G. & SEVASTOPULO, G. 2010. The correlation poten- tial of magnetic susceptibility and outcrop gamma-ray logs at sults from the Moravian Karst (Zukalová 1980, Dvořák Tournaisian-Viséan boundary sections in western Europe. 1985, Hladil 2002, Racki et al. 2002) and southern Poland Geologica Belgica 13, 291–307. (Racki et al. 2002, Pujol et al. 2006, Rakociński et al. BÁBEK, O., KALVODA, J., COSSEY, P., ŠIMÍČEK, D., DEVUYST, F.X. 2016). MS values display a close link with siliciclastic con- &HARGREAVES, S. 2013. Facies and petrophysical signature tent (Fig. 7) and are therefore considered as proxy of silici- of the Tournaisian/Viséan (Lower Carboniferous) sea-level clastic influx across Fr-Fa boundary interval in the Mo- cycle in carbonate ramp to basinal settings of the ravian Karst sections. U/Th increase in the LKWI and Wales–Brabant massif, British Isles. Sedimentary Geology UKWI of the Steinbruch Schmidt section (Fig. 7) supports 284-285, 197–213. DOI 10.1016/j.sedgeo.2012.12.008 previously interpreted dysoxic to anoxic conditions (e.g. BÁBEK, O., KUMPAN, T., KALVODA,J.&MATYS GRYGAR, T. 2016. Pujol et al. 2006) during the deposition in the event inter- Devonian/Carboniferous boundary glacioeustatic fluctuations vals. U concentrations are also generaly high in the studied in a platform-to-basin direction: A geochemical approach of sequence stratigraphy in pelagic settings. Sedimentary Geol- Moravian Karst sections. Higher U content is probably re- ogy 337, 81–99. DOI 10.1016/j.sedgeo.2016.03.009 lated to a detritic fraction rich in U (good correlation with BÁBEK, O., PŘIKRYL,T.&HLADIL, J. 2007. Progressive drowning siliciclastic content proxies). Enrichment in palaeoproduc- of carbonate platform in the Moravo-Silesian Basin (Czech tivity proxies (Zn, Pb) appears only in the LKWI and Republic) before the Frasnian/Famennian event: facies, UKWI of the Steinbruch Schmidt section, whereas only re- compositional variations and gamma ray spectrometry. Facies lative increases in Zn and Pb were documented in the 53(2), 293–316. DOI 10.1007/s10347-006-0095-8 (Upper?) Kellwasser interval from the Lesní lom and Šum- BOND, D.P.G. & WIGNALL, P. 2008. The role of sea-level change bera sections. and marine anoxia in the Frasnian-Famennian (Late Devon- ian) mass extinction. Palaeogeography, Palaeoclimatology, Palaeoecology 263, 107–118. Acknowledgements DOI 10.1016/j.palaeo.2008.02.015 BOND,D.&ZATOŃ, M. 2003. Gamma-ray spectrometry across the Upper Devonian basin succession at Kowala in the Holy Cross The reviewers Marek Narkiewicz and Michał Rakociński Mountains (Poland). Acta Geologica Polonica 53, 93–99. are thanked for their helpful suggestions. This research BOND, D., WIGNALL,P.B.&RACKI, G. 2004. Extent and duration was supported by the Czech Science Foundation project of marine anoxia during the Frasnian–Famennian (Late Dev- GA14-18183S and is a contribution to the International onian) mass extinction in Poland, Germany, Austria and Geoscience Programme (IGCP) Project 652 – Reading geo- France. Geological Magazine 141(2), 173–193. logic time in Paleozoic sedimentary rocks. DOI 10.1017/S0016756804008866 BOND, D.P.G., ZATOŃ, M., WIGNALL, P.B. & MARYNOWSKI,L. 2013. Evidence for shallow water ‘Upper Kellwasser’ anoxia References in the Frasnian–Famennian reefs of Alberta, Canada. Lethaia 46, 355–368. DOI 10.1111/let.12014 ADACHI, N., EZAKI,Y.&LIU, J. 2004. The fabrics and origin of BRATTON, J.F., BERRY, W.B.N. & MORROW, J.R. 1999. Anoxia peloids immediately after the end-Permian extinction, predates Frasnian-Famennian boundary mass extinction Guizhou Province, South China. Sedimentary Geology 164, horizont in the Great Basin, USA. Palaeogeography, 161–178. DOI 10.1016/j.sedgeo.2003.10.007 Palaeoclimatology, Palaeoecology 154, 275–292. ALEKSEEV, A.S., KONONOVA,L.I.&NIKISHIN, A.M. 1996. The Dev- DOI 10.1016/S0031-0182(99)00116-9 onian and Carboniferous of the Moscow Syneclise (Russian BRETT, C.E., MCLAUGHLIN, P.I., SCHINDLER, E., HISTON,K.&

275 Bulletin of Geosciences • Vol. 92, 2, 2017

FERRETTI, A. 2012. Time specific aspects of facies: State of the amples from the Devonian of Belgium. Sedimentology 56, art, examples, and possible causes. Palaeogeography, 1292–1306. DOI 10.1111/j.1365-3091.2008.01034.x Palaeocliamtology, Palaeoecology 367–368, 6–18. DEAN, W.E. 2007. Sediment geochemical records of productivity DOI 10.1016/j.palaeo.2012.10.009 and oxygen depletion along the margin of western North BRUMSACK, H.J. 2006. The trace metal content of recent organic America during the past 60,000 years: teleconnections with carbon-rich sediments: Implications for Cretaceous black Greenland Ice and the Cariaco Basin. Quaternary Science Re- shale formation. Palaeogeography, Palaeoclimatology, views 26, 98–114. DOI 10.1016/j.quascirev.2006.08.006 Palaeoecology 232, 344–361. DE VLEESCHOUWER, D., CRICIFIX, M., BOUNCEUR,N.&CLAEYS,P. DOI 10.1016/j.palaeo.2005.05.011 2014. The impact of astronomical forcing on the Late Devon- BUGGISCH, W. 1972. Zur Geologie und Geochemie der ian greenhouse climate. Global and Planetary Change 120, Kellwasserkalke und ihrer begleitenden Sedimente (Unteres 65–80. DOI 10.1016/j.gloplacha.2014.06.002 Oberdevon). Abhandlungen des Hessischen Landesamtes für DEVLEESCHOUWER, X., HERBOSCH,A.&PRÉAT, A. 2002. Micro- Bodenforschung 62, 1–68. facies, sequence stratigraphy and clay mineralogy of a con- CALVERT,S.E.&PEDERSEN, T.F. 1993. Geochemistry of recent densed deep-water section around the Frasnian/Famennian oxic and anoxic marine sediments – implications for the geo- boundary (Steinbruch Schmidt, Germany). Palaeogeography, logical record. Marine Geology 113, 67–88. Palaeoclimatology, Palaeoecology 181, 171–193. DOI 10.1016/0025-3227(93)90150-T DOI 10.1016/S0031-0182(01)00478-3 CASIER, J.G. & LETHIERS, F. 1998. Ostracods late Devonian mass DEVLEESCHOUWER, X., RIQUIER, L., BÁBEK, O., DE VLEESHOUWER, extinction; the Schmidt Quarry parastratotype (Kellerwald, D., PETITCLERC, E., STERCKX,S.&SPASSOV, S. 2015. Magneti- Germany). Comptes Rendus de l’Académie des Sci- zation carriers of grey to red deep-water limestones in the ences/Earth and Planetary Science 326, 71–78. GSSP of the Givetian–Frasnian boundary (Puech de la Suque, CHEN,D.&TUCKER, M.E. 2004. Palaeokarst and its implication France): signals influenced by moderate diagenetic overprint- for the extinction event at the Frasnian-Famennian boundary ing, 245–256. In DA SILVA, A.C., WHALEN, M.T., HLADIL, J., (Guilin, south China). Journal of the Geological Society, Lon- CHADIMOVÁ, L., CHEN, D., SPASSOV, S., BOULVAIN,F.& don 161, 895–898. DOI 10.1144/0016-764904-035 DEVLEESCHOUWER, X. (eds) Magnetic Susceptibility Applica- CHEN, D., QING,H.&LI, R. 2005. The Late Devonian tion: A Window onto Ancient Environments and Climatic Frasnian-Famennian (F/F) biotic crisis: insights from Variations. Geological Society of London, Special Publica- 13 13 87 86 Ccarb, Corg and Sr / Sr isotopic systems. Earth and tions 414. DOI 10.1144/SP414.15 Planetary Science Letters 235, 151–166. DOPIERALSKA, J., BELKA,Z.&WALCZAK, A. 2016. Nd isotope DOI 10.1016/j.epsl.2005.03.018 composition of conodonts: An accurate proxy of sea-level CHOW,N.&GEORGE, A.D. 2004. Tepee-shaped agglutinated fluctuations. Gondwana Research 34, 284–295. microbialites: an example from a Famennian carbonate plat- DOI 10.1016/j.gr.2015.02.022 form on the Lennard Shelf, northern Canning Basin, Western DOVETON, J.H. & MERRIAM, D.F. 2004. Borehole petrophysical Australia. Sedimentology 51, 253–265. chemostratigraphy of Pennsylvanian black shales in the Kan- DOI 10.1046/j.1365-3091.2003.00620.x sas subsurface. Chemical Geology 206, 249–258. COLLIN, P.Y., KERSHAW, S., TRIBOVILLARD, N., FOREL, M.B. & DOI 10.1016/j.chemgeo.2003.12.027 CRASQUIN, S. 2015. Geochemistry of post-extinction micro- DVOŘÁK, J. 1985. Tektogeneze devonu a spodního karbonu bialites as a powerful tool to assess the oxygenation of shallow Hornoslezské pánve. Zemní plyn a Nafta 30(1), 1–14. marine water in the immediate aftermath of the end-Permian DYPVIK,H.&HARRIS, N.B. 2001. Geochemical facies analysis of mass extinction. International Journal of Earth Sciences 104, fine-grained siliciclastics using Th/U, Zr/Rb and (Zr+Rb/Sr) 1025–1037. DOI 10.1007/s00531-014-1125-3 ratios. Chemical Geology 181, 131–146. COPPER, P. 2002. Reef development at the Frasnian-Famennian DOI 10.1016/S0009-2541(01)00278-9 mass extinction boundary. Palaeogeography, Palaeoclimato- ELLWOOD, B.B., CRICK, R.E., EL HASSANI, A., BENOIST, S.L. & logy, Palaeoecology 181, 27–66. YOUNG, R.H. 2000. Magnetosusceptibility event and DOI 10.1016/S0031-0182(01)00472-2 cyclostratigraphy method applied to marine rocks: detrital in- CRICK, R.E., ELLWOOD, B.B., FEIST, R., EL HASSANI, A., SCHINDLER, put versus carbonate productivity. Geology 28, 1135–1138. E., DREESEN, R., OVER,D.J.&GIRARD, C. 2002. DOI 10.1130/0091-7613(2000)28<1135:MEACMA>2.0.CO;2 Magnetostratigraphy susceptibility of the Frasnian/Famennian FEIST, R. 1985. Devonian stratigraphy of the South-eastern boundary. Palaeogeography, Palaeoclimatology, Palaeoecol- Montagne Noire (France). Courier Forschungsinstitut ogy 181, 67–90. DOI 10.1016/S0031-0182(01)00473-4 Senckenberg 75, 331–352. DA SILVA, A.C., DE VLEESCHOUWER, D., BOULVAIN, F., CLAEYS, P., FEIST,R.&SCHINDLER, E. 1994. Trilobites during the Frasnian FAGEL, N., HUMBLET, M., MABILLE, C., MICHEL, J., SARDAR Kellwasser Cisis in European Late Devonian cephalopod ABADI, M., PAS,D.&DEKKERS, M.J. 2013. Magnetic suscepti- limestones. Courier Forschungsinstitut Senckenberg 169, bility as a high-resolution correlation tool and as a climatic 195–223. proxy in Paleozoic rocks – Merits and pitfalls: Examples from FRALICK,P.W.&KRONBERG, B.I. 1997. Geochemical discrimina- the Devonian in Belgium. Marine and Petroleum Geology 46, tion of clastic sedimentary rock sources. Sedimentary Geology 173–189. DOI 10.1016/j.marpetgeo.2013.06.012 113, 111–124. DOI 10.1016/S0037-0738(97)00049-3 DA SILVA, A.C., MABILLE,C.&BOULVAIN, F. 2009. Influence of FRANKE, W. 1995. III.A Introduction, 29–30. In DALLMEYER, sedimentary setting on the use of magnetic susceptibility: ex- R.D., FRANKE,W.&WEBER, K. (eds) Pre-Permian Geology of

276 TomᚠWeiner et al. • An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval

Central and Eastern Europe. Springer, Berlin, Heidelberg, products on the Frasnian carbonate platform and early New York. Famennian ramps in Moravia, Czech Republic: proxies for FRANKE, W. 2002. The mid-European segment of the Variscides: eustasy and palaeoclimate. Palaeogeography, Palaeo- tectonostratigraphic units, terrane boundaries and plate tec- climatology, Palaeoecology 181, 213–250. tonic evolution, 35–61. In WINCHESTER, J.A., PHARAOH, T.C. DOI 10.1016/S0031-0182(01)00480-1 &VERNIERS, J. (eds) Palaeozoic amalgamation of Central HLADIL,J.,&KALVODA, J. 1993a. Devonian boundary intervals of Europe. Geological Society of London, Special Publications Bohemia and Moravia especially the Eifelian/Givetian and 201. Frasnian/Famenian events with respect to the Silurian/Devon- GEORGE, A.D., CHOW,N.&TRINAJSTIC, K.M. 2014. Oxic facies ian and Devonian/Carboniferous boundaries, 29–50. In and the Late Devonian mass extinction, Canning Basin, Aus- NARKIEWICZ, M. (ed.) Global boundary events. Excursion tralia. Geology 42, 327–330. DOI 10.1130/G35249.1 guidebook, Warszawa. GEREKE, M. 2007. Die oberdevonische Kellwasser-Krise in der HLADIL,J.&KALVODA, J. 1993b. Extinction and recovery succes- Beckenfazies von Rhenoherzynikum und Saxothuringikum sions on the Devonian marine shoals: the Eifelian-Givetian (spätes Frasnium/frühestes Famennium, Deutschland). Kölner and Frasnian-Famennian events in Moravia and Bohemia. Forum für Geologie und Paläontologie 17, 1–228. Věstník Českého geologického ústavu 68(4), 13–23. GEREKE,M.&SCHINDLER, E. 2012. “Time-Specific Facies” and HLADIL, J., GERSL, M., STRNAD, L., FRANA, J., LANGROVA,A.& biological crises – The Kellwasser Event interval near the SPISIAK, J. 2006. Stratigraphic variation of complex impurities Frasnian/Famennian boundary (Late Devonian). Palaeogeog- in platform limestones and possible significance of atmo- raphy, Palaeoclimatology, Palaeoecology 367–368, 19–29. spheric dust: a study with emphasis on gamma-ray spectrome- DOI 10.1016/j.palaeo.2011.11.024 try and magnetic susceptibility outcrop logging GEREKE, M., LUPPOLD, F.W., PIECHA, M., SCHINDLER,E.& (Eifelian-Frasnian, Moravia, Czech Republic). International STOPPEL, D. 2014. Die Typlokalität der Kellwasser-Horizonte Journal of Earth Sciences 95(4), 703–723. im Oberharz, Deutschland. Zeitschrift der Deutschen DOI 10.1007/s00531-005-0052-8 Gesellschaft für Geowissenschaften, 165(2), 145–162. HLADIL, J., KREJCI, Z., KALVODA, J., GINTER, M., GALLE,A.& DOI 10.1127/1860-1804/2014/0066 BEROUSEK, P. 1991. Carbonate ramp environment of GILÍKOVÁ, H., LEICHMANN,J.&BURIÁNEK, D. 2006. Record of Kellwasser time-interval; Lesni lom, Moravia, Czechoslova- sialic volcanism found in the Devonian clastic sediments at the kia. Bulletin de la Société Belge de Géologie 100(1-2), eastern margin of the Bohemian Massif. Geologické Výzkumy 57–119. na Moravě a ve Slezsku v roce 2005, 72–74. HOUSE, M.R. 2002. Strength, timing, setting and cause of mid- GIRARD, C. 1995. Les biofaciès à conodontes à la limite Palaeozoic extinctions. Palaeogeography, Palaeoclima- Frasnien/Famennien en Montagne Noire (France). Implica- tology, Palaeoecology 181, 5–25. tions stratigraphiques. Comptes Rendus de l’Académie des DOI 10.1016/S0031-0182(01)00471-0 Sciences/Series II a 321, 689-692. HUANG,C.&GONG, Y. 2016. Timing and patterns of the GIRARD,C.&FEIST, R. 1997. Eustatic trends in conodont diver- Frasnian-Famennian event: Evidences from high-resolution sity across the Frasnian-Famennian boundary in the stratotype conodont biostratigraphy and event stratigraphy at the Yangdi area, Montagne Noire, Southern France. Lethaia 29, 329–337. section, Guangxi, South China. Palaeogeography, DOI 10.1111/j.1502-3931.1996.tb01668.x Palaeoclimatology, Palaeoecology 448, 317–338. GRIMM, M.C. 1998. Systematik und Paläoökologie der DOI 10.1016/j.palaeo.2015.10.031 Buchiolinae nov. subfam. Schweizerische Paläontologische JANOUŠEK, V., AICHLER, J., HANŽL, P., GERDES, A., ERBAN, V., Abhandlungen 118, 1–176. ŽÁČEK, V., PECINA, V., PUDILOVÁ, M., HRDLIČKOVÁ, K., MIXA, GROOS-UFFENORDE,H.&SCHINDLER, E. 1990. The effect of P.&ŽÁČKOVÁ, E. 2014. Constraining genesis and global events on entomozoacean ostracods, 101–112. In geotectonic setting of metavolcanic complexes: a multi- WHATLEY,R.&MAYBURY, C. (eds) Ostracoda and Global disciplinary study of the Devonian Vrbno Group (Hrubý Events. British Micropalaeontological Society Publication Jeseník Mts., Czech Republic). International Journal of Series. Springer Chapman & Hall, London. Earth Sciences 103, 455–483. HALGEDAHL, S.L., JARRARD, R.D., BRETT,C.E.&ALLISON, P.A. DOI 10.1007/s00531-013-0975-4 2009. Geophysical and geological signatures of relative sea JOACHIMSKI, M.M. & BUGGISCH, W. 1993. Anoxic events in the level change in the upper Wheeler Formation, Drum Moun- late Frasnian – Causes of the Frasnian-Famennian faunal cri- tains, West-Central Utah: A perspective into exceptional pres- sis? Geology 21, 675–678. ervation of fossils. Palaeogeography, Palaeoclimatology, DOI 10.1130/0091-7613(1993)021<0675:AEITLF>2.3.CO;2 18 Palaeoecology 277(1-2), 34–56. JOACHIMSKI, M.M. & BUGGISCH, W. 2002. Conodont apatite δ O DOI 10.1016/j.palaeo.2009.02.011 signatures indicate climatic cooling as a trigger of the Late HALLAM,A.&WIGNALL, P.B. 1997. Mass Extinctions and Their Devonian mass extinctions. Geology 30, 711–714. Aftermath. 325 pp. Oxford University Press, Oxford. DOI 10.1130/0091-7613(2002)030<0711:CAOSIC>2.0.CO;2 HIPS,K.&HAAS, J. 2006. Calcimicrobial stromatolites at the JOACHIMSKI, M.M., OSTERTAG-HENNING, C., PANCOST, R.D., Permian–Triassic boundary in a western Tethyan section, STRAUSS, H., FREEMAN, K.H., LITTKE, R., SINNINGHE DAMSTÉ, Bükk Mountains, Hungary. Sedimentary Geology 185, J.S. & RACKI, G. 2001. Water column anoxia, enhanced pro- 239–253. DOI 10.1016/j.sedgeo.2005.12.016 ductivity and concomitant changes in δ13C and δ34S across the HLADIL, J. 2002. Geophysical records of dispersed weathering Frasnian-Famennian boundary (Kowala – Holy Cross Moun-

277 Bulletin of Geosciences • Vol. 92, 2, 2017

tains/Poland). Chemical Geology 175, 109–131. lation with the Carnic Alps (Austria). Geological Magazine DOI 10.1016/S0009-2541(00)00365-X 151, 201–215. DOI 10.1017/S0016756812001057 JOACHIMSKI, M.M., PANCOST, R.D., FREEMAN, K.H., OSTERTAG- KUMPAN, T., BÁBEK, O., KALVODA, J., MATYS GRYGAR,T.& HENNING,C.&BUGGISCH, W. 2002: Carbon isotope geochem- FRÝDA, J. 2014b. Sea-level and environmental changes around istry of the Frasnian-Famennian transition. Palaeogeography, the Devonian–Carboniferous boundary in the Namur–Dinant Palaeoclimatology, Palaeoecology 181, 91–109. Basin (S Belgium, NE France): a multi-proxy stratigraphic DOI 10.1016/S0031-0182(01)00474-6 analysis of carbonate ramp archives and its use in regional and JONES,B.&MANNING, D.A.C. 1994. Comparison of geochemical interregional correlations. Sedimentary Geology 311, 43–59. indices used for the interpretation of paleoredox conditions in DOI 10.1016/j.sedgeo.2014.06.007 ancient mudstone. Chemical Geology 111, 111–129. KUMPAN, T., BÁBEK, O., KALVODA, J., MATYS GRYGAR, T., FRÝDA, DOI 10.1016/0009-2541(94)90085-X J., BECKER,R.T.&HARTENFELS, S. 2015. Petrophysical and JONES, A.F., MACKLIN, M.G. & BREWER, P.A. 2012. A geochemi- geochemical signature of the Hangenberg Events: an inte- cal record of flooding on the upper River Severn, UK, during grated stratigraphy of the Devonian–Carboniferous boundary the last 3750 years. Geomorphology 179, 89–105. interval in the Northern Rhenish Massif (Avalonia, Germany). DOI 10.1016/j.geomorph.2012.08.003 Bulletin of Geosciences 90(3), 667–694. KALVODA, J. 1998. The main phases of extension in the eastern DOI 10.3140/bull.geosci.1547 part of the Rhenohercynian zone. Acta Universitatis LAZREQ, N. 1999. Biostratigraphie des conodontes du Givétien au Carolinae, Geologica 42(2), 274–275. Famennien du Maroc Central. Biofaciès et événement KALVODA, J. 2002. Late Devonian–Early Carboniferous Kellwasser. Courier Forschungsinstitut Senckenberg 214, foraminiferal fauna: zonation, evolutionary events, paleo- 1–111. biogeography and tectonic implications. Folia 39, 1–213. LI, Y.X. 2000. Famennian tentaculitids of China. Journal of Pale- KALVODA, J., BÁBEK, O., FATKA, O., LEICHMANN, J., MELICHAR,R. ontology 74(5), 969–975. DOI 10.1017/S0022336000033138 &ŠPAČEK, P. 2008. Brunovistulian terrane (Bohemian Massif, LÜNING, S., ADAMSON,K.&CRAIG, J. 2003. Frasnian organic-rich Central Europe) from late Proterozoic to late Paleozoic: a re- shales in North Africa: regional distribution and depositional view. International Journal of Earth Sciences 97, 497–517. model, 165–184. In ARTUR, T., MACGREGOR,D.S.&CAMERON, DOI 10.1007/s00531-007-0183-1 N.R. (eds) Petroleum Geology of Africa: New Themes and De- KAMBER, B.S., BULHAR,R.&WEBB, G.E. 2004. Geochemistry of veloping Technologies. Geological Society of London, Special late Archaean stromatolites from Zimbabwe: evidence for Publications 207. microbial life in restricted epicontinental seas. Precambrian LÜNING, S., WENDT, J., BELKA,Z.&KAUFMANN, B. 2004. Tempo- Research 132, 379–399. ral-spatial reconstruction of the early Frasnian (Late Devon- DOI 10.1016/j.precamres.2004.03.006 ian) anoxia in NW Africa; new field data from the Ahnet Basin KAUFMANN, B., TRAPP,E.&MEZGER, K. 2004. The Numerical (Algeria). Sedimentary Geology 163, 237–264. Age of the Upper Frasnian (Upper Devonian) Kellwasser Ho- DOI 10.1016/S0037-0738(03)00210-0 rizons: A New U-Pb Zircon Date from Steinbruch Schmidt LYONS,T.W.&SEVERMANN, S. 2006. A critical look at iron (Kellerwald, Germany). The Journal of Geology 112, paleoredox proxies: New insights from modern euxinic ma- 495–501. DOI 10.1086/421077 rine basins. Geochimica et Cosmochimica Acta 70, KIESSLING, W., FLÜGEL,E.&GOLONKA, J. 2000. Fluctuations in 5698–5722. DOI 10.1016/j.gca.2006.08.021 the carbonate production of Phanerozoic reefs, 191–215. In MARYNOWSKI, L., RAKOCIŃSKI, M., BORCUCH, E., KREMER, B., INSALACO, E., SKELTON,P.W&PALMER, J.T. (eds) Carbonate SCHUBERT, B.A. & JAHREN, A.H. 2011. Molecular and Platform Systems: Components and Interactions. Geological petrographic indicators of redox conditions and bacterial com- Society of London, Special Publications 178. munities after the F/F mass extinction (Kowala, Holy Cross KLAPPER, G. 2007. Conodont taxonomy and the recognition of the Mountains, Poland). Palaeogeography, Palaeoclimatology, Frasnian/Famennian (Upper Devonian) Stage Boundary. Stra- Palaeoecology 306, 1–14. DOI 10.1016/j.palaeo.2011.03.018 tigraphy 4(1), 67–76. MARYNOWSKI, L., ZATOŃ, M., RAKOCIŃSKI, M., FILIPIAK, P., KLAPPER, G., FEIST, R., BECKER,R.T.&HOUSE, M.R. 1993. Defi- KURKIEWICZ,S.&PEARCE, T.J. 2012. Deciphering the upper nition of the Frasnian/Famennian Stage boundary. Episodes Famennian Hangenberg Black Shale depositional environ- 16(4), 433–441. ments based on multi-proxy record. Palaeogeography, KOPTÍKOVÁ, L., BÁBEK, O., HLADIL, J., KALVODA,J.&SLAVÍK,L. Palaeoclimatology, Palaeoecology 346–347, 66–86. 2010. Stratigraphic significance and resolution of spectral DOI 10.1016/j.palaeo.2012.05.020 reflectance logs in Lower Devonian carbonates of the MATYJA,H.&NARKIEWICZ, M. 1992. Conodont biofacies succes- Barrandian area, Czech Republic; a correlation with magnetic sion near the Frasnian/Famennian boundary – Some Polish ex- susceptibility and gamma-ray logs. Sedimentary Geology 225, amples. Courier Forschungsinstitut Senckenberg 154, 83–98. DOI 10.1016/j.sedgeo.2010.01.004 125–147. KRMÍČEK, L. 2006. Petrologický výzkum hádského slepence. 109 MAYNARD, J.B. 2005. Manganiferous Sediments, Rocks, and pp. Master thesis, Masaryk University, Brno, Czech Republic. Ores, 289–308. In MACKENZIE, F.T. (ed.) Sediments, KUMPAN, T., BÁBEK, O., KALVODA, J., FRÝDA,J.&MATYS Diagenesis, and Sedimentary Rocks, Treatise on Geochemis- GRYGAR, T. 2014a. A high-resolution, multiproxy strati- try 7. Elsevier, Amsterdam. graphic analysis of the Devonian–Carboniferous boundary MCGHEE, G.R. JR. 1996. The Late Devonian Mass Extinction. sections in the Moravian Karst (Czech Republic) and a corre- The Frasnian–Famennian Crisis. 303 pp. Columbia University

278 TomᚠWeiner et al. • An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval

Press, New York. Palaeoclimatology, Palaeoecology 240, 120–145. DOI 10.7312/columbia/9780231160575.001.0001 DOI 10.1016/j.palaeo.2006.03.055 MCGHEE, G.R. JR. 2013. When the Invasion of Land Failed. The RABIEN, A. 1956. Zur Stratigraphie und Fazies des Oberdevons in Legacy of the Devonian Extinctions, 317 pp. Columbia Uni- der Waldecker Hauptmulde. Abhandlungen des hessischen versity Press, New York. Landesamtes für Bodenforschung 16, 1–83. MCLAREN, D.J. 1970. Presidential address: time, life and bound- RACHOLD,V.&BRUMSACK, H.J. 2001. Inorganic geochemistry of aries. Journal of Paleontology 48, 801–815. Albian sediments from the Lower Saxony basin, NW Ger- MEISCHNER, D. 1971. Clastic sedimentation in the Variscan many: paleoenvironmental constraints and orbital cycles. geosyncline east of the River Rhine, 9–43. In MÜLLER, G. (ed.) Palaeogeography, Palaeoclimatology, Palaeoecology 174, Sedimentology of Parts of Central Europe. International 123–144. DOI 10.1016/S0031-0182(01)00290-5 Sedimentological Congress, Guidebook 8, Heidelberg. RACKI, G. 2005. Towards understanding Late Devonian global MORFORD, J.L., MARTIN, W.R., FRANCOIS,R.&CARNEY, C.M. events: few answers, many questions, 5–36. In OVER, D.J., 2009. A model for uranium, rhenium, and molybdenum MORROW,J.R.&WIGNALL, P.B. (eds) Understanding Late De- diagenesis in marine sediments based on results from coastal vonian and Permian–Triassic Biotic and Climatic Events: To- locations. Geochimica et Cosmochimica Acta 73, 2938–2960. wards an Integrated Approach. Developments in Palaeontol- DOI 10.1016/j.gca.2009.02.029 ogy and Stratigraphy Series 20. Elsevier, Amsterdam. MURPHY, A.E., SAGEMAN, B.B., HOLLANDER, D.J., LYONS, T.W. & RACKI, G. 2012. The Alvarez impact theory of mass extinction; BRETT, C.E. 2000. Black shale deposition and faunal overturn limits to its applicability and the “great expectations syn- in the Devonian Appalachian basin: clastic starvation, sea- drome”. Acta Palaeontologica Polonica 57(4), 681–702. sonal water column mixing, and efficient biolimiting nutrient DOI 10.4202/app.2011.0058 recycling. Paleoceanography 15, 280–291. RACKI, G., BALIŃSKI, A., WRONA, R., MAŁKOWSKI, K., DRYGANT, DOI 10.1029/1999PA000445 D.&SZANIAWSKI, H. 2012. Faunal dynamics across the Silur- 13 18 NIEBUHR, B. 2005. Geochemistry and time-series analyses of or- ian–Devonian positive isotope excursions (δ C, δ O) in bitally forced Upper Cretaceous marl-limestone rhythmites Podolia, Ukraine: Comparative analysis of the Ireviken and (Lehrte West Syncline, northern Germany). Geological Maga- Klonk events. Acta Palaeontologica Polonica 57(4), zine 142, 31–55. DOI 10.1017/S0016756804009999 795–832. DOI 10.4202/app.2011.0206 NOVÁKOVÁ, T., MATYS GRYGAR, T., BÁBEK, O., FAMĚRA, M., RACKI, G., RACKA, M., MATYJA,H.&DEVLEESCHOUWER, X. 2002. MIHALJEVIČ,M.&STRNAD, L. 2013. Distinguishing regional The Frasnian/Famennian boundary interval in the South Pol- and local sources of pollution by trace metals and magnetic ish-Moravian shelf basins: integrated event-stratigraphical ap- particles in fluvial sediments of the Morava River, Czech Re- proach. Palaeogeography Palaeoclimatology Palaeoecology public. Journal of Soils and Sediments 13, 460–473. 181, 251–297. DOI 10.1016/S0031-0182(01)00481-3 DOI 10.1007/s11368-012-0632-8 RAKOCIŃSKI,M.&RACKI, G. 2016. Microbialites in the shal- OLEMPSKA, E. 2002. The Late Devonian Upper Kellwasser Event low-water marine environments of the Holy Cross Mountains and entomozoacean ostracods in the Holy Cross Mountains, (Poland) in the aftermath of the Frasnian–Famennian biotic Poland. Acta Palaeontologica Polonica 47(2), 247–266. cisis. Global and Planetary Change 136, 30–40. OVER, D.J. 2002. The Frasnian/Famennian boundary in central DOI 10.1016/j.gloplacha.2015.12.001 and eastern United States. Palaeogeography, Palaeoclima- RAKOCIŃSKI, M., PISARZOWSKA, A., JANISZEWSKA,K.&SZREK,P. tology, Palaeoecology 181, 153–169. 2016. Depositional conditions during the Lower Kellwasser DOI 10.1016/S0031-0182(01)00477-1 Event (Late Frasnian) in the deep-shelf Łysogory Basin of the OVER,D.J.&SCHINDLER, E. 2003. Depositional similarities in se- Holy Cross Mountains Poland. Lethaia 49, 571–590. lected Late Devonian Kellwasser Horizons: Germany, Mo- DOI 10.1111/let.12167. rocco, and Eastern United States. Geological Society of Amer- RIDER, M.H. 1999. The Geological Interpretation of Well Logs. ica, Abstracts with Programs 35(6), 384. 288 pp. Whittles Publishing Services, Dunbeath. PLANK,T.&LANGMUIR, C.H. 1998. The geochemical composi- RIQUIER, L., AVERBUCH, O., DEVLEESCHOUWER,X.&TRIBO- tion of subducting sediment and its consequences for the crust VILLARD, N. 2009. Diagenetic versus detrital origin of the mag- and mantle. Chemical Geology 145, 325–394. netic susceptibility variations in some carbonate Frasn- DOI 10.1016/S0009-2541(97)00150-2 ian–Famennian boundary sections from Northern Africa and POSENATO, R., HOLMER, L.E. & PRINOTH, H. 2014. Adaptive strat- Western Europe: implications for paleoenvironmental recon- egies and environmental significance of lingulid brachiopods structions. International Journal of Earth Sciences 99, 57–73. across the late Permian extinction. Palaeogeography, DOI 10.1007/s00531-009-0492-7 Palaeoclimatology, Palaeoecology 399, 373–384. RIQUIER, L., TRIBOVILLARD, N., AVERBUCH, O., DEVLEESCHOUWER, DOI 10.1016/j.palaeo.2014.01.028 X.&RIBOULLEAU, A. 2006. The Late Frasnian Kellwasser ho- PŘICHYSTAL, A. 1993. Paleozoic to Quaternary volcanism in the rizons of the Harz Mountains (Germany): two oxygen-defi- geological history of Moravia and Silesia, 59–70. In cient periods resulting from different mechanisms. Chemical PŘICHYSTAL, A., OBSTOVÁ,V.&SUK, M. (eds) Geologie Geology 233, 137–155. DOI 10.1016/j.chemgeo.2006.02.021 Moravy a Slezska, Faculty of Sciences, Masaryk University. RIQUIER, L., TRIBOVILLARD, N., AVERBUCH, O., JOACHIMSKI, M.M., PUJOL, F., BERNER,D.&STÜBEN, D. 2006. Palaeoenvironmental RACKI, G., DEVLEESCHOUWER, X., EL ALBANI,A.& changes at the Frasnian/Famennian boundary in key European RIBOULLEAU, A. 2005. Productivity and bottom water redox sections: Chemostratigraphic constraints. Palaeogeography, conditions at the Frasnian–Famennian boundary on both sides

279 Bulletin of Geosciences • Vol. 92, 2, 2017

of the Eovariscan Belt: constraints from trace element geo- frühen Famenne-Stufe (Conodonta, Oberdevon). Göttinger chemistry, 199–224. In OVER, D.J., MORROW,J.R.&WIGNALL, Arbeiten zur Geologie und Paläontologie 67, 1–108. P.B. (eds) Understanding Late Devonian and Permian–Trias- SCHULTE,P.&SPEIJER, R.P. 2009. Late Maastrichtian-Early sic biotic and climatic events: towards an integrated ap- Paleocene sea level and climate changes in the Antioch proach. Developments in Palaeontology and Stratigraphy 20. Church Core (Alabama, Gulf of Mexico margin, USA): Elsevier, Amsterdam. A multi-proxy approach. Geologica Acta 7, 11–34. RUFFELL,A.&WORDEN, R. 2000. Palaeoclimate analysis using SDIRI, A.T., HIGASHI,T.&JAMOUSSI, F. 2014. Adsorption of cop- spectral gamma-ray data from the Aptian (Cretaceous) of per and zinc onto natural clay in single and binary systéme. In- southern England and southern France. Palaeogeography, ternational Journal of Environmental Science and Technology Palaeoclimatology, Palaeoecology 155, 265–283. 11, 1081–1092. DOI 10.1007/s13762-013-0305-1 DOI 10.1016/S0031-0182(99)00119-4 SHEN, J.W., WEBB, G.E. 2008. The role of microbes in reef-build- SAGEMAN,B.B.&LYONS, T.W. 2005. Geochemistry of ing communities of the Cannindah limestone (Mississippian), fine-grained sediments and sedimentary rocks, 115–158. In Monto region, Queensland, Australia. Facies 54, 89–105. MACKENZIE, F.T. (ed.) Sediments, Diagenesis, and Sedimen- DOI 10.1007/s10347-007-0116-2 tary Rocks, Treatise on Geochemistry 7. Elsevier, Amsterdam. SHEN, J.W., WEBB, G.E. & JELL, J.S. 2008. Platform margins, reef SANDBERG, C.A., ZIEGLER, W., DREESEN,R.&BUTLER, J.L. 1988. facies, and microbial carbonates; a comparison of Devonian Late Frasnian mass extinction: conodont event stratigraphy, reef complexes in the Canning Basin, Western Australia, and global changes, and possible causes. Courier Forschungs- the Guilin region, South China. Earth-Science Reviews 88, institut Senckenberg 102, 263–307. 33–59. DOI 10.1016/j.earscirev.2008.01.002 SCHINDLER, E. 1988. Stop B 12 Aeke valley. Courier SHEN, J.W., WEBB, G.E. & QING, H. 2010. Microbial mounds Forschungsinstitut Senckenberg 102, 211–213. prior to the Frasnian-Famennian mass extinctions, Hantang, SCHINDLER, E. 1990a. The Late Frasnian (Upper Devonian) Guilin, South China. Sedimentology 57, 1615–1639. Kellwasser Crisis. Lecture Notes in Earth Sciences 30, DOI 10.1111/j.1365-3091.2010.01158.x 151–159. DOI 10.1007/BFb0011143 ŚLIWIŃSKI, M.G., WHALEN,M.T.&DAY, J. 2010. Trace element SCHINDLER, E. 1990b. Die Kellwasser-Krise (hohe Frasne-Stufe, variations in the Middle Frasnian punctata Zone (Late Dev- Ober-Devon). Göttinger Arbeiten zur Geologie und onian) in the western Canada sedimentary basin – changes Paläontologie 46, 1–115. in oceanic bioproductivity and paleoredox spurred by SCHINDLER, E. 1993. Event-stratigraphical markers within the a pulse of terrestrial afforestation? Geologica Belgica Kellwasser Crisis near the Frasnian/Famennian boundary 13(4), 459–482. (Upper Devonian) in Germany. Palaeogeography, SPALLETTA, C., PERRI, M.C., OVER, D.J. & CORRADINI, C. 2017. Palaeoclimatology, Palaeoecology 104, 115–125. Famennian (Upper Devonian) conodont zonation: revised DOI 10.1016/0031-0182(93)90124-2 global standard. Bulletin of Geosciences 92(1), 31–57. SCHINDLER, E. 2012. Tentaculitoids – an enigmatic group of DOI 10.3140/bull.geosci.1623 Palaeozoic fossils, 479–490. In TALENT, J.A. (ed.) Earth and ŠTELCL, J. 1969. Polymiktní slepence z Hádů u Brna. Folia Life: Global Biodiversity, Extinction Intervals and Univerisitatis Purkynianae brunensis, Geologia 19, 3–38. Biogeographic Perturbations Through Time. Springer, STREITOVÁ, M. 1994. Hranice frasnu a famenu mezi Hády a Šum- Dordrecht, Heidelberg, London, New York. berovou skálou v jižní části Moravského krasu. Geologické DOI 10.1007/978-90-481-3428-1 výzkumy na Moravě a ve Slezsku v roce 1993, 65–66. SCHINDLER, E., SCHÜLKE,I.&ZIEGLER, W. 1998. The SZULCZEWSKI, M. 1989. Swiatowe I regionalne zdarzenia w za- Frasnian/Famennian boundary at the Sessacker Trench section pisie stratygraficznym pogranicza franu I famenu Gór near Oberscheld (Dill Syncline, Rheinisches Schiefergebirge, Swietodrzyskich. Przeglad geologiczny 11, 551–557. Germany). Senckenbergiana lethaea, 77(1-2), 243–261. TAYLOR, S.R. & MCLENNAN, S.M. 1985. The Continental Crust: SCHLEGEL, M.S., MANCEAU, A., CHARLET, L., CHATEIGNER,D.& Its Composition and Evolution. 312 pp. Blackwell, Palo Alto. HAZEMANN, J.L. 2001. Sorption of metal ions on clay minerals. TRIBOVILLARD, N., ALGEO, T.J., LYONS,T.&RIBOULLEAU,A. III. Nucleation and epitaxial growth of Zn phyllosilicate on the 2006. Trace metals as paleoredox and paleoproductivity proxies: edges of hectorite. Geochimica et Cosmochimica Acta 65(22), An update. Chemical Geology 232, 12–32. 4155–4170. DOI 10.1016/S0016-7037(01)00700-1 DOI 10.1016/j.chemgeo.2006.02.012 SCHMIDT, H. 1925. Schwellen- und Beckenfazies im TRIBOVILLARD, N., AVERBUCH, O., DEVLEESCHOUWER, X., RACKI, ostrheinischen Paläozoikum. Zeitschrift der Deutschen G. & RIBOLLEAU, A. 2004. Deep-water anoxia over the Geologischen Gesellschaft 77, 226–234. Frasnian–Famennian boundary (La Serre, France): a tectoni- SCHMIDT, H. 1935. Die bionomische Einteilung der fossilen cally induced oceanic anoxic event? Terra Nova 16, 288–295. Meeresböden. Fortschritte der Geologie und Paläontologie DOI 10.1111/j.1365-3121.2004.00562.x 12, 1–154. TUCKER, M.E. 1974. Sedimentology of Palaeozoic pelagic lime- SCHNETGER, B., BRUMSACK, H.J., SCHALE, H., HINRICHS,J.& stones: The Devonian Griotte (Southern France) and DITTERT, L. 2000. Geochemical characteristics of deep-sea Cephalopodenkalk (Germany), 71–92. In HSÜ, K.J. & sediments from the Arabian Sea: a high-resolution study. JENKYNS, H.C. (eds) Pelagic Sediments: on Land and under Deep Sea Research II: Topical Studies in Oceanography 47, the Sea. Special Publication of the International Association 2735–2768. DOI 10.1016/S0967-0645(00)00047-3 of Sedimentologists 1. Blackwell, Oxford. SCHÜLKE, I. 1995. Evolutive Prozesse bei Palmatolepis in der DOI 10.1002/9781444304855.ch4

280 TomᚠWeiner et al. • An Integrated Stratigraphy of the Frasnian-Famennian Boundary Interval

TUCKER, M.E. & WRIGHT, V.P. 1990. Carbonate depositional sys- Environments and Climatic Variations. Geological Society of tems II: deeper-water facies of pelagic and resedimented lime- London, Special Publications 414. stones, 228–283. In TUCKER, M.E. & WRIGHT, V.P. (eds) Car- WIGNALL, P.B. & MYERS, K.J. 1988. Interpreting benthic oxygen bonate Sedimentology. Blackwell, Oxford. levels in mudrocks: a new approach. Geology 16, 452–455. VAN DERWEIJDEN, C.H. 2002. Pitfalls of normalization of marine DOI 10.1130/0091-7613(1988)016<0452:IBOLIM>2.3.CO;2 geochemical data using a common divisor. Marine Geology WOOD, R. 2000. Palaeoecology of a Late Devonian back reef: 184, 167–187. DOI 10.1016/S0025-3227(01)00297-3 Canning Basin, Western Australia. Palaeontology 43(4), WALLISER, O.H. 1984a. Geologic processes and global events. 671–703. DOI 10.1111/1475-4983.00145 Terra Cognita 4, 17–20. WOOD, R. 2004. Palaeoecology of a post-extinction reef: WALLISER, O.H. 1984b. Pleading for a natural D/C-boundary. Famennian (Late Devonian) of the Canning Basin, Courier Forschungsinstitut Senckenberg 67, 241–246. North-Western Australia. Palaeontology 47(2), 415–445. WALLISER, O.H. 1986. The IGCP Project 216 “Global Biological DOI 10.1111/j.0031-0239.2004.00373.x Events in Earth History”. Lecture Notes in Earth Sciences 8, YUDINA, B.A., RACKI, G., SAVAGE, N.M., RACKA,M.& 1–4. DOI 10.1007/BFb0010186 MAŁKOWSKI, K. 2002. The Frasnian–Famennian events, Sub- WALLISER, O.H. 1996. Global events in the Devonian and Carbon- polar Urals: biotic, depositional, and geochemical records. iferous, 225–250. In WALLISER, O.H. (ed.) Global events and Acta Palaeontologica Polonica 47, 355–372. event stratigraphy in the Phanerozoic. Springer, Berlin. ZATOŃ, M., ZHURAVLEV, A.V., RAKOCIŃSKI, M., FILIPIAK, P., WENDT,J.&BELKA, Z. 1991. Age and depositional environment BORSZCZ, T., KRAWCZYŃSKI, W., WILSON,M.A.&SOKIRAN, of Upper Devonian (Early Frasnian to Early Famennian) black E.V. 2014. Microconchid-dominated cobbles from the Up- shales and limestones (Kellwasser Facies) in the eastern per Devonian of Russia: opportunism and dominance in a Anti-Atlas, Morocco. Facies 25, 51–90. restricted environment following the Frasnian-Famennian DOI 10.1007/BF02536755 biotic crisis. Palaeogeography, Palaeoclimatology, WHALEN, M.T. & DAY, J. 2010. Cross-basin variations in mag- Palaeoecology 401, 142–153. netic susceptibility infuenced by changing sea level, DOI 10.1016/j.palaeo.2014.02.029 paleogeography, and paleoclimate: upper Devonian, Western ZHENG, Y., ANDERSON, R.F., VAN GEEN,A.&FLEISHER, M.Q. Canada. Journal of Sedimentary Research 80, 1109–1127. 2002. Preservation of nonlithogenic particulate uranium in DOI 10.2110/jsr.2010.093 marine sediments. Geochimica et Cosmochimica Acta 66, WHALEN, M.T., DAY, J., EBERLI, G.P. & HOMEWOOD, P.W. 2002. 3085–3092. DOI 10.1016/S0016-7037(01)00632-9 Microbial carbonates as indicators of environmental change ZIEGLER, W. (1962): Taxonomie und Phylogenie oberdevonischer and biotic crises in carbonate systems: examples from the Late Conodonten und ihre stratigraphische Bedeutung. Abhand- Devonian, Alberta Basin, Canada. Palaeogeography, lungen des hessischen Landesamtes für Bodenforschung 38, Palaeoclimatology, Palaeoecology 181, 127–151. 1–166. DOI 10.1016/S0031-0182(01)00476-X ZIEGLER, W. (1969): Eine neue Conodontenfauna aus dem WHALEN, M.T., ŚLIWIŃSKI, M.G., PAYNE, J.H., DAY, J.E., CHEN,D. höhsten Oberdevon. Fortschritte Geologie von Rheinland und &DA SILVA, A.C. 2015. Chemostratigraphy and magnetic sus- Westfalen 17, 171–191. ceptibility of the Late Devonian Frasnian–Famennian transi- ZIEGLER,W.&SANDBERG, C.A. 1990. The Late Devonian Cono- tion in western Canada and southern China: implications for dont Standard Zonation. Courier Forschungsinstitut Sencken- carbon and nutrient cycling and mass extinction, 37–72. In DA berg 121, 1–115. SILVA, A.C., WHALEN, M.T., HLADIL, J., CHADIMOVA, L., CHEN, ZUKALOVÁ, V. 1980. Stromatoporoids in the Devonian carbonate D., SPASSOV, S., BOULVAIN,F.&DEVLEESCHOUWER, X. (eds) complex in Moravia (Czechoslovakia). Acta Palaeontologica Magnetic Susceptibility Application: A Window onto Ancient Polonica 25, 671–679.

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